JP2009263316A - Method for producing incompletely condensed oligosilsesquioxane - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new method for producing an incompletely condensed POSS (polyhedral oligosilsesquioxane) derivative by reshuffling of a completely condensed POSS skeleton. <P>SOLUTION: The method for producing an incompletely condensed POSS derivative is provided, comprising subjecting a completely condensed octaphenyl octasilsesquioxane of general formula (1) (wherein, Ph is a phenyl group) to hydrolysis reaction in a water-alcohol solvent in the presence of an alkali. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a method for producing incompletely condensed oligosilsesquioxane.

The incompletely condensed oligosilsesquioxane skeleton plays an important role as a synthesis block for a polymer containing silsesquioxane, a silica-supported catalyst, a network polymer and the like (for example, Non-Patent Document 1). Regarding the synthesis of incompletely condensed polyhedral oligosilsesquioxane (hereinafter sometimes referred to as POSS), Feher et al. Have attempted “controlled cleavage” of a fully condensed POSS skeleton (for example, Non-Patent Document 2).
Macromolecules 2007, 40, 16, 5698-5705 Journal of the American Chemical Society (J. Am. Chem. Soc.) 1997, 119, 46, 11323-11324

The present invention is to provide a novel production method for obtaining a cyclic tetramer and an incompletely condensed POSS derivative by reshuffling process of a fully condensed POSS skeleton.

The present invention relates to a general formula (1)

[Wherein Ph represents a phenyl group. ]
A fully condensed octaphenyl octasilsesquioxane (hereinafter sometimes referred to as Ph-T ₈ ) represented by the following formula is hydrolyzed in the presence of an alkali in a water-alcohol solvent, and then protected with a protecting group as necessary. General formula (2) characterized by

[式中、Ｒ’はフェニル基を表し、Ｒ’’はナトリウム（Ｎａ）又はＳｉ（Ｒ’’’）_３を表し、Ｒ’’’は水素、炭素数１から４の脂肪族炭化水素基又は更に置換基を有することもあるフェニル基を表す。]
で示される環状ヘプタシルセスキオキサン及び／又は一般式（４）

[式中、Ｒ’はフェニル基を表し、Ｒ’’はナトリウム（Ｎａ）又はＳｉ（Ｒ’’’）_３を表し、Ｒ’’’は水素、炭素数１から４の脂肪族炭化水素基又は更に置換基を有することもあるフェニル基を表す。]
で示される環状オクタシルセスキオキサンの製造方法である（請求項１）。 [Wherein R ′ represents a phenyl group, R ″ represents sodium (Na) or Si (R ′ ″) ₃ , R ′ ″ represents hydrogen, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Or it represents the phenyl group which may have a substituent further. ]
A cyclic tetrasiloxane represented by the general formula (3)

[Wherein R ′ represents a phenyl group, R ″ represents sodium (Na) or Si (R ′ ″) ₃ , R ′ ″ represents hydrogen, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Or it represents the phenyl group which may have a substituent further. ]
Cyclic heptasilsesquioxane and / or general formula (4)

Wherein, R 'represents a phenyl group, R''is sodium (Na) or Si (R''') ₃ represents, R '''is hydrogen, an aliphatic hydrocarbon group having 1 to 4 carbon atoms Or it represents the phenyl group which may have a substituent further. ]
(Claim 1) It is a manufacturing method of cyclic octasilsesquioxane shown by these.

Moreover, this invention is a manufacturing method of Claim 1 as which alcohol is selected from the C1-C4 aliphatic alcohol which may be branched (Claim 2).

Furthermore, the present invention relates to a quaternary ammonium salt in which the alkali is an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate, an alkaline earth metal carbonate, or an alkyl substituent having 1 to 4 carbon atoms. The production method according to any one of claims 1 to 2, wherein the production method is selected from the hydroxides of quaternary ammonium salts having an alkyl substituent of 1 to 4 carbon atoms.

[式中、Ｐｈはフェニル基を表す。]
で示される完全縮合オクタフェニルオクタシルセスキオキサン（Ｐｈ−Ｔ_８）を、水−アルコール溶媒中、アルカリの共存下、加水分解反応させ、次いで保護基（クロロトリメチルシランなどのシランカップリング剤）で保護することを特徴とする一般式（５）

[式中、R’はフェニル（Ph）を表す。]
で示される環状１，３，５，７−テトラキス（トリメチルシリル）テトラフェニルテトラシロキサン（Ｔ_４ＯＴＭＳ）、一般式（６）

[式中、R’はフェニル（Ph）を表す。]
で示される環状３，７，１４−トリス（トリメチルシリル）ヘプタフェニルトリシクロ［７．３．３．１^５，１１］ヘプタシルセスキオキサン（Ｔ_７ＯＴＭＳ）及び／又は一般式（７）

[式中、R’はフェニル（Ph）を表す。]
で示される環状５，１１，１４，１７−テトラキス（トリメチルシリル）オクタフェニルテトラシクロ［７．３．３．３^３，７］オクタシルセスキオキサン（ＤＤＴ_８ＯＴＭＳ）の製造方法である（請求項５）。 Furthermore, the present invention is the production method according to any one of claims 1 to 3, wherein the reaction temperature is selected from the range of room temperature to the reflux temperature of the solvent (claim 4).
Next, the present invention provides a general formula (1)

[Wherein Ph represents a phenyl group. ]
Is fully condensed octaphenyl octasilsesquioxane (Ph-T ₈ ) in a water-alcohol solvent in the presence of an alkali, followed by a hydrolysis reaction, and then a protective group (a silane coupling agent such as chlorotrimethylsilane). General formula (5) characterized by protection with

[Wherein, R ′ represents phenyl (Ph). ]
Cyclic 1,3,5,7-tetrakis (trimethylsilyl) tetraphenyltetrasiloxane (T ₄ OTMS) represented by the general formula (6)

[Wherein, R ′ represents phenyl (Ph). ]
In shown are annular 3,7,14- tris (trimethylsilyl) heptaphenyl tricyclo ^{[7.3.3.1 5 and 11]} hept silsesquioxane _(T 7 OTMS) and / or formula (7)

[Wherein, R ′ represents phenyl (Ph). ]
A cyclic 5,11,14,17-tetrakis (trimethylsilyl) octaphenyltetracyclo [7.3.3.3 ^3,7 ] octasilsesquioxane (DDT ₈ OTMS) represented by 5).

The present invention is to provide a novel production method for obtaining a cyclic tetramer, an incompletely condensed POSS derivative by rearrangement of the skeleton of a fully condensed POSS. The feature of the present invention is that the cyclic molar ratio of the water-alcohol solvent and alkali, the reaction temperature, and the like are arbitrarily changed, so that the cyclic tetrasiloxane (cyclic tetramer skeleton) of the above general formula (2) It is to provide a novel production method for obtaining arbitrarily cyclic hepta silsesquioxane (T ₇ backbone) and incomplete condensation POSS derivatives of cyclic octasilsesquioxane of general formula (4) (DDT ₈ backbone) of).

As described above, the present invention relates to the general formula (1)

[Wherein Ph represents a phenyl group. ]
A fully condensed octaphenyl octasilsesquioxane (Ph-T ₈ ) represented by the formula (1) is hydrolyzed in the presence of an alkali in a water-alcohol solvent, and then protected with a protecting group, if necessary. General formula (2)

[式中、Ｒ’はフェニル基を表し、Ｒ’’はナトリウム（Ｎａ）又はＳｉ（Ｒ’’’）_３を表し、Ｒ’’’は水素、炭素数１から４の脂肪族炭化水素基又は更に置換基を有することもあるフェニル基を表す。]
で示される環状ヘプタシルセスキオキサン及び／又は一般式（４）

[式中、Ｒ’はフェニル基を表し、Ｒ’’はナトリウム（Ｎａ）又はＳｉ（Ｒ’’’）_３を表し、Ｒ’’’は水素、炭素数１から４の脂肪族炭化水素基又は更に置換基を有することもあるフェニル基を表す。]
で示される環状オクタシルセスキオキサンの製造方法である。
中でも、本発明は、一般式（１）

[式中、Ｐｈはフェニル基を表す。]
で示される完全縮合オクタフェニルオクタシルセスキオキサン（Ｐｈ−Ｔ_８）を、水−アルコール溶媒中、アルカリの共存下、加水分解反応させ、次いで保護基（クロロトリメチルシランなどのシランカップリング剤）で保護することを特徴とする一般式（５）

[式中、R’はフェニル（Ph）を表す。]
で示される環状１，３，５，７−テトラキス（トリメチルシリル）テトラフェニルテトラシロキサン（Ｔ_４ＯＴＭＳ）、一般式（６）

[式中、R’はフェニル（Ph）を表す。]
で示される環状３，７，１４−トリス（トリメチルシリル）ヘプタフェニルトリシクロ［７．３．３．１^５，１１］ヘプタシルセスキオキサン（Ｔ_７ＯＴＭＳ）及び／又は一般式（７）

[式中、R’はフェニル（Ph）を表す。]
で示される環状５，１１，１４，１７−テトラキス（トリメチルシリル）オクタフェニルテトラシクロ［７．３．３．３^３，７］オクタシルセスキオキサン（ＤＤＴ_８ＯＴＭＳ）の製造方法である。 [Wherein R ′ represents a phenyl group, R ″ represents sodium (Na) or Si (R ′ ″) ₃ , R ′ ″ represents hydrogen, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Or it represents the phenyl group which may have a substituent further. ]
A cyclic tetrasiloxane represented by the general formula (3)

[Wherein R ′ represents a phenyl group, R ″ represents sodium (Na) or Si (R ′ ″) ₃ , R ′ ″ represents hydrogen, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Or it represents the phenyl group which may have a substituent further. ]
Cyclic heptasilsesquioxane and / or general formula (4)

[Wherein R ′ represents a phenyl group, R ″ represents sodium (Na) or Si (R ′ ″) ₃ , R ′ ″ represents hydrogen, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Or it represents the phenyl group which may have a substituent further. ]
It is a manufacturing method of cyclic octasilsesquioxane shown by these.
Among these, the present invention provides the general formula (1)

[Wherein Ph represents a phenyl group. ]
Is fully condensed octaphenyl octasilsesquioxane (Ph-T ₈ ) in a water-alcohol solvent in the presence of an alkali, followed by a hydrolysis reaction, and then a protective group (a silane coupling agent such as chlorotrimethylsilane). General formula (5) characterized by protection with

[Wherein, R ′ represents phenyl (Ph). ]
Cyclic 1,3,5,7-tetrakis (trimethylsilyl) tetraphenyltetrasiloxane (T ₄ OTMS) represented by the general formula (6)

[Wherein, R ′ represents phenyl (Ph). ]
In shown are annular 3,7,14- tris (trimethylsilyl) heptaphenyl tricyclo ^{[7.3.3.1 5 and 11]} hept silsesquioxane _(T 7 OTMS) and / or formula (7)

[Wherein, R ′ represents phenyl (Ph). ]
In shown are annular 5,11,14,17- tetrakis (trimethylsilyl) octaphenyl tetracyclo [7.3.3.3 ^{3, 7]} is a manufacturing method of octasilsesquioxane _(DDT 8 OTMS).

Hereinafter, the details of the hydrolysis reaction mechanism of the present invention will be described more specifically.
In the hydrolysis of fully condensed octaphenyl octasilsesquioxane (Ph-T ₈ ) with sodium hydroxide in water-alcohol, depending on the reaction temperature and the ratio of starting materials, cyclic tetramer, DDT ₈ , T ₇ skeleton can be obtained selectively. The synthesis results are shown in Table 1.

ａ；Ｐｈ−Ｔ_８／溶媒＝１ｍｍｏｌ／６ｍＬ
ｂ；Ｐｈ−Ｔ_８／溶媒＝１ｍｍｏｌ／１０ｍＬ

a; Ph-T ₈ / solvent = 1 mmol / 6 mL
b; Ph-T ₈ / solvent = 1 mmol / 10 mL

Hydrolysis of Ph-T ₈ with water and sodium hydroxide (Ph-T ₈ : H ₂ O: NaOH = 1: 2: 4 molar ratio) in 2-propanol at room temperature for 40 hours, followed by trimethylchlorosilane Upon treatment, a cis-form cyclic tetramer (T ₄ OTMS) was obtained as the main product (Table 1, No. 1).

1- [Bis (trimethylsiloxy)] phenyl-3,5,7-tris (trimethylsiloxy) -1,3,5,7-tetraphenylcyclosiloxane is obtained by hydrolysis of Ph-T ₈ followed by room temperature. Obtained by protection of the trimethylsilyl (TMS) group. This fact suggests cleavage of the bridging portion of the Ph-T _8, and a gradual cleavage of the annular portion.

DDT ₈ OTMS, which is a double-decker POSS, can be obtained in high yields by refluxing in 2-propanol or hydrolysis in 2-methyl-1-propanol at 90 ° C. for 24 hours (Table 1, No. .2 and 3).

When the molar ratio of the starting materials (Ph-T ₈ : H ₂ O: NaOH) was changed from 1: 2: 4 to 1: 1: 2, 3,7,14-tris (trimethylsilyl) heptaphenyltricyclo “7. 3.3.1 ^5,11 "Heptasilsesquioxane (T ₇ OTMS) is obtained as the main product (Table 1, No. 4).

Hereinafter, the actual hydrolysis reaction of the present invention will be described more specifically.

Specific examples of the aliphatic alcohol having 1 to 4 carbon atoms which may be used in the production method of the present invention include ethanol, 2-propanol, 2-methyl-1-propanol, n-butanol or Examples include Sec-butanol. Of these, 2-propanol or 2-methyl-1-propanol is preferably used.

Examples of the alkali used in the production method of the present invention include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, and four alkyl substituents having 1 to 4 carbon atoms. Selected from hydroxides of quaternary ammonium salts and fluorides of quaternary ammonium salts having an alkyl substituent of 1 to 4 carbon atoms, specifically, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate Etc. Of these, sodium hydroxide is preferably used.

In the production method of the present invention, the reaction temperature is selected within the range of room temperature to the reflux temperature of the water-alcohol solvent.

In the production method of the present invention, the object is taken out and separated by an ordinary method such as a crystallization method or a concentration to dryness method.

Hereinafter, the method of the present invention will be described more specifically with reference to examples.

Example 1
A 100 mL two-necked flask containing Ph-T ₈ (4.14 g, 4 mmol) and sodium hydroxide (0.64 g, 16 mmol) was purged with nitrogen. Subsequently, 2-propanol (24 mL) and water (8 mmol) were added to the reactor and stirred at room temperature for 40 hours. After completion of the reaction, a white solid was obtained by filtration, washed with 2-propanol, and dried at 70 ° C. under vacuum. In order to facilitate the identification of the product, the ONa group was protected with a trimethylsilyl group by the following experimental procedure.

The above product (1.20 g) was added to a 100 mL two-necked flask and the atmosphere was replaced with nitrogen in the same manner. In an ice-water bath, tetrahydrofuran (THF; 10 mL), triethylamine (1.8 g, 17.8 mmol) and chlorotrimethylsilane (2.3 g, 21.2 mmol) were added to the reactor, and the reaction solution was stirred at room temperature for 3 hours. Water (10 mL) was slowly added to the reactor under an ice water bath. Stirring was stopped and the organic layer was separated, washed with distilled water to neutralize, and hexane (10 mL) was added to the organic layer. An insoluble solid precipitated in an organic solvent or water, and this was identified as unreacted Ph-T ₈ from silicon nuclear magnetic resonance measurement ( ²⁹ Si-NMR; δ = 78.31 ppm).

As a result, the conversion of _{Ph-T 8} was 77%. 1,3,5,7-tetra (trimethylsiloxy) -1,3,5,7-tetraphenylcyclosiloxane (T ₄ OTMS) was obtained by preparative size exclusion chromatography (SEC) as a trimethylsilyl protected product. It was. The weight ratio of T ₄ OTMS in the total composition was 50%.

1- [Bis (trimethylsiloxy)] phenyl-3,5,7-tris (trimethylsiloxy) -1,3,5,7-tetraphenylcyclosiloxane is matrix-assisted laser desorption ionization-time-of-flight mass spectrometer The spectrum obtained from (MALDI-TOF-MS) is shown in FIG. 1 [MALDI-TOF-MS (m / z): 1073.84 [M + Na] ⁺ , calc. 1073.26].

The SEC chromatogram before fractionation, Mw / Mn = 1940/1860 (26.17%); 1090/1080 (73.83%) is shown in FIG. The SEC chromatogram after fractionation is Mw / Mn = 1960/1050.

The compound identification data is shown below.
Elemental analysis: C% 51.82 (found), 51.38 (calc.); H% 6.53 (found), 6.71 (calc.).
MALDI-TOF-MS (m / z): 863.94 ([M + Na] ⁺ calc. 863.20).
²⁹ Si-NMR δ (ppm): 10.51 (OSiMe ₃ ), −79.66 (O ₃ SiPh).

Example 2
The procedure was the same as the reaction at room temperature except that the mixture was stirred for 24 hours under reflux. After completion of the reaction, a white solid was obtained by filtration, washed with 2-propanol, and dried at 70 ° C. under vacuum. The resulting product was 5,11,14,17-tetra (sodio) octaphenyltetracyclo [7.3.3.3 ^3,7 ] octasilsesquioxanolate (DDT ₈ ONa). Yield: 4.21 g (91% yield). To facilitate product identification, the ONa group was protected with a trimethylsilyl group by the following experimental procedure. The above product (0.61 g, 0.53 mmol) was added to a 100 mL two-necked flask, and the atmosphere was replaced with nitrogen in the same manner. Under an ice-water bath, THF (10 mL), triethylamine (1.8 g, 17.8 mmol), and chlorotrimethylsilane (2.3 g, 21.2 mmol) were added to the reactor. The reaction solution was stirred at room temperature for 3 hours, and water (10 mL) was slowly added to the reactor in an ice-water bath. Stirring was stopped and the organic layer was separated, washed with distilled water to neutralize, and hexane (10 mL) was added to the organic layer. The organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off to obtain a white solid. Yield: 0.52 g (72% yield). Single crystals were obtained by slowly evaporating the solvent in a hexane solution containing the product and determined by single crystal X-ray diffraction (shown in FIG. 3). The product was analyzed by elemental analysis, SEC, MALDI-TOF-MS, ²⁹ Si-NMR, single crystal X-ray diffraction, 5,11,14,17-tetrakis (trimethylsilyl) octaphenyltetracyclo [7.3.3.3. ^3,7 ] octasilsesquioxane (DDT ₈ OTMS).

The compound identification data is shown below.
Elemental analysis: C% 53.92 (found), 53.06 (calc.); H% 5.83 (found), 5.64 (calc.).
SEC: Mw / Mn = 1240/1230.
MALDI-TOF-MS (m / z): 1379.60 ([M + Na] ⁺ , calc. 1379.24).
²⁹ Si-NMR δ (ppm): 10.51 (OSiMe ₃ ); −76.10, −78.95 (O ₃ SiPh).

Example 3
When 2-methyl-1-propanol was used as a solvent and the reaction was stirred at 90 ° C. under the same conditions as in Example 2, DDT ₈ OTMS was obtained in 69% yield.

Example 4
The molar ratio of Ph-T ₈ : H ₂ O: NaOH was changed from 1: 2: 4 to 1: 1: 2, Ph-T ₈ / 2-propanol was changed from 1 mmol / 6 mL to 1 mmol / 10 mL, and other conditions Were reacted in the same manner, and 3,7,14-tris (trimethylsilyl) heptaphenyltricyclo [7.3.3.3 ^5,11 ] heptacilsesquioxane (T ₇ OTMS) was 44% as the main product. Obtained in yield.

The compound identification data is shown below.
MALDI-TOF-MS (m / z): 1169.55 ([M + Na] ⁺ calc. 1169.18).
²⁹ Si-NMR δ (ppm): 10.54 (OSiMe ₃ ); −77.62, −77.99, −78.26 (O ₃ SiPh).

These POSSs are expected as synthetic elements for applications such as various resists and pattern forming materials, oxygen absorbers and oxygen-absorbing resin compositions, and plasma display panels.

3 shows MALDI-TOF-MS of a product obtained by hydrolyzing Ph-T ₈ protected with a trimethylsilyl group at room temperature. Example 1 At room temperature and Ph-T ₈ that trimethylsilyl groups protected, shows the SEC of the product obtained by hydrolysis. Example 1 An ORTEP (Oak Ridge Thermal Ellipoid Plot) plot obtained by using single crystal X-ray crystal structure diffraction for a product obtained by hydrolyzing Ph-T ₈ protected with a trimethylsilyl group under reflux is shown. (Example 2)

Claims (5)

General formula (1)

[Wherein Ph represents a phenyl group. ]
A fully condensed octaphenyl octasilsesquioxane (Ph-T ₈ ) represented by the formula (1) is hydrolyzed in the presence of an alkali in a water-alcohol solvent, and then protected with a protecting group as necessary General formula (2)

[Wherein R ′ represents a phenyl group, R ″ represents sodium (Na) or Si (R ′ ″) ₃ , R ′ ″ represents hydrogen, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Or it represents the phenyl group which may have a substituent further. ]
A cyclic tetrasiloxane represented by the general formula (3)

[Wherein R ′ represents a phenyl group, R ″ represents sodium (Na) or Si (R ′ ″) ₃ , R ′ ″ represents hydrogen, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Or it represents the phenyl group which may have a substituent further. ]
Cyclic heptasilsesquioxane and / or general formula (4)

[Wherein R ′ represents a phenyl group, R ″ represents sodium (Na) or Si (R ′ ″) ₃ , R ′ ″ represents hydrogen, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Or it represents the phenyl group which may have a substituent further. ]
The manufacturing method of cyclic octasilsesquioxane shown by these. The production method according to claim 1, wherein the alcohol is selected from aliphatic alcohols having 1 to 4 carbon atoms which may be branched. Alkali is alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, alkaline earth metal carbonate, quaternary ammonium salt hydroxide and carbon having an alkyl substituent of 1 to 4 carbon atoms and carbon The production method according to any one of claims 1 to 2, wherein the production method is selected from fluorides of quaternary ammonium salts having an alkyl substituent of 1 to 4. The production method according to any one of claims 1 to 3, wherein the reaction temperature is selected from the range of room temperature to the reflux temperature of the solvent. General formula (1)

[Wherein Ph represents a phenyl group. ]
Is fully condensed octaphenyl octasilsesquioxane (Ph-T ₈ ) in a water-alcohol solvent in the presence of an alkali, followed by a hydrolysis reaction, and then a protective group (a silane coupling agent such as chlorotrimethylsilane). General formula (5) characterized by protection with

[Wherein, R ′ represents phenyl (Ph). ]
Cyclic 1,3,5,7-tetrakis (trimethylsilyl) tetraphenyltetrasiloxane (T ₄ OTMS) represented by the general formula (6)

[Wherein, R ′ represents phenyl (Ph). ]
In shown are annular 3,7,14- tris (trimethylsilyl) heptaphenyl tricyclo ^{[7.3.3.1 5 and 11]} hept silsesquioxane _(T 7 OTMS) and / or formula (7)

[Wherein, R ′ represents phenyl (Ph). ]
Method for producing in shown are annular 5,11,14,17- tetrakis (trimethylsilyl) octaphenyl tetracyclo [7.3.3.3 ^{3, 7]} octasilsesquioxane _(DDT 8 OTMS).

Images