JP3453592B2 - Method for alkoxylation, aralkyloxylation or aryloxylation of hydridosilsesquioxanes - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a part or all of hydrogen on silicon of a hydridosilsesquioxane which is useful as a heat resistant material or a flame retardant material, and an alkoxy group,
The present invention relates to a method for synthesizing a compound substituted with an aralkyloxy group or an allyloxy group. These compounds are
It is also useful as a raw material for producing coatings and highly porous ceramics by the sol-gel method [eg J. Inor
g. Organomet. Polym., 1 (3), 335-342 (1991).].

[0002]

A typical example of alkoxylated hydridosilsesquioxane, which is represented by the formula (2)

[Chemical 3] Octakis (methoxysilsesquioxane)
Is due to the fact that it is hydrolyzable.₈O₂₀
^8-Cannot be prepared by alkylation of
Yes. To that end, Octakis (hydridosilsesquioki)
Sun) [(HSiO _3/2)₈] With chlorine under light irradiation
Chlorinated (ClSiO_3/2)₈And sublimation
After manufacturing, add methyl nitrite or methyl orthoformate to
By a dangerous multi-step reaction using chlorine.
[J. Am. Chem. Soc., 107 (26), 8262
-8264 (1985)]. With trimethyltin methoxide,
Octakis (hydridosilsesquioxane) [(HSi
O_3/2)₈There is also a method of directly methoxylating
Use of poisonous tin compounds and reagents and byproducts
It is a method with many drawbacks that reacts and becomes a by-product.
[J. Inorg. Organomet. Polym., 1 (3), 335-342 (199
1).].

[0003]

DISCLOSURE OF THE INVENTION The present invention is directed to the formation of hydrogen on the silicon of hydridosilsesquioxanes by an alkoxy group,
It is intended to provide a safe and convenient method for substituting an aralkyloxy group or an aryloxy group.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to solve the above-mentioned problems, and as a result, have reacted hydridosilsesquioxanes with alcohols or hydroxyarenes to give hydrides. The present invention has been completed by finding a method for substituting hydrogen on silicon of silsesquioxanes with an alkoxy group, an aralkyloxy group, or an aryloxy group.

That is, the present invention is characterized in that alcohols or hydroxyarenes are used in the presence of a transition metal-containing catalyst, and the general formula (1) is used.

[Chemical 4] (In the formula, n represents a positive integer of 6 or more.), A hydridosilsesquioxane or a mixture thereof,
Part or all of hydrogen on silicon is an RO group (wherein R represents an alkyl group, an aralkyl group, or an aryl group,
They may be different from each other. ) To how to change.

The hydridosilsesquioxane in the present invention may be any one represented by the general formula (1) (n is a positive integer of 6 or more).
Examples of those in which n is relatively small include octakis (hydridosilsesquioxane) (n = 8 in Formula 1), decaquis (hydridosilsesquioxane) (Formula 1,
n = 10), dodecaquis (hydridosilsesquioxane) (n = 12 in formula 1), tetradecaquis (hydridosilsesquioxane) (n = 1 in formula 1)
4), hexadecakis (hydridosilsesquioxane)
(In the formula 1, n = 16) or octadecakis (hydridosilsesquioxane) (in the formula 1, n =
18) and the like. These usually have a cage structure, but those having a relatively large n include those having various structures. Further, a mixture of these plural kinds of hydridosilsesquioxanes may be used.

As the alcohols or hydroxyarenes of the present invention, various ones are used, and examples thereof include methanol, ethanol, n-propanol, isopropyl alcohol, n-butyl alcohol,
sec-butyl alcohol, isobutyl alcohol, t
-Butyl alcohol, cyclohexyl alcohol, octanols, 2-methoxyethanol, 2-ethoxyethanol, alcohols such as diethylene glycol methyl ether, diethylene glycol ethyl ether, arcols such as benzyl alcohol, phenol, cresols, methoxyphenols, naphthol, etc. The hydroxyarenes of

Examples of the transition metal-containing catalyst used in the present invention include titanium-containing catalyst, zirconium-containing catalyst, ruthenium-containing catalyst, cobalt-containing catalyst, iridium-containing catalyst, platinum-containing catalyst and copper-containing catalyst. Specific examples of the titanium-containing catalyst include a mixture of bis (cyclopentadienyl) dichlorotitanium and an alkyllithium compound, a mixture of bis (pentamethylcyclopentadienyl) dichlorotitanium and an alkyllithium compound, and cyclopentadiene. Mixtures of enyltrichlorotitanium and alkyllithium compounds, bis (cyclopentadienyl) dimethyltitanium, bis (cyclopentadienyl) titanium dicarbonyl, bis (t-butylcyclopentadienyl) dimethyltitanium, titanium tetra (isopropoxy) ), Titanium diisopropoxide bis (acetylacetonato), pentamethylcyclopentadienyltrimethoxytitanium, titanium tetra-n-butoxide, tris (acetylacetonato)
Examples include titanium. Examples of zirconium-containing catalysts include bis (cyclopentadienyl) dimethylzirconium, [dimethylsilylenebis (cyclopentadienyl)] dimethylzirconium, bis (cyclopentadienyl) hydridochlorozirconium, and bis (cyclopentadienyl) dichlorozirconium. And a mixture of an alkyllithium compound, a mixture of bis (pentamethylcyclopentadienyl) dichlorozirconium and an alkyllithium compound, zirconium tetrakis (t-butoxide), zirconium tetra-n-butoxide, tetrakis (acetylacetonato) zirconium, etc. Is mentioned. Examples of the ruthenium-containing catalyst include tris (triphenylphosphine) dichlororuthenium, triruthenium dodecacarbonyl, ruthenium tris (acetylacetonato), dichlorotricarbonylruthenium dimer, dichloro (1,5-cyclooctadiene) ruthenium, bis ( Examples of the cobalt-containing catalyst such as cyclopentadienyl) ruthenium include dicobalt octacarbonyl, a mixture of dicobalt octacarbonyl and triphenylphosphine, bis (triphenylphosphine) dicobalt hexacarbonyl, bis (triethylphosphine) dicobalt hexa. Carbonyl, cobalt tris (acetylacetonato), bis (cyclopentadienyl) cobalt, cyclopentadienylcobalt dicarbonyl and the like include iridium-containing catalysts such as bis (cyclopentadienyl) cobalt. Triphenylphosphine) carbonylchloroiridium, (1,5-cyclooctadiene) chloroiridium, hydridocarbonyltris (triphenylphosphine) iridium, iridiumcarbonyl, etc. As platinum-containing catalysts, bis (cyclooctadiene) platinum, tris ( Divinyltetramethyldisiloxane) diplatinum, bis (triphenylphosphine) dichloroplatinum, bis (benzonitrile) dichloroplatinum, (1,5
-Cyclooctadiene) dichloroplatinum, diamminedichloroplatinum, dimethyl (1,5-cyclooctadiene) platinum, tetrakis (triphenylphosphine) platinum, ethylenebis (triphenylphosphine) platinum, platinum chloride, etc. , Hydridotriphenylphosphine copper hexamer, bis (acetylacetonato) copper, copper acetate and the like.

In the reaction of the present invention, the alcohol used in the reaction can be used as a solvent, but a solvent capable of dissolving hydridosilsesquioxane may be used. Examples of these solvents are hexane, benzene, toluene,
THF, dioxane, chloroform and the like can be mentioned. The reaction temperature is not particularly limited, but considering the reaction rate, etc.,
It is preferably 0 ° C. to 120 ° C., more preferably it is carried out at a temperature from room temperature to 80 ° C.

The ratio of the alcohols to the hydridosilsesquioxane in the reaction of the present invention is not particularly limited and can be arbitrarily set in consideration of the substitution rate and the reaction rate. It is necessary to use more than an equivalent amount of alcohol to replace all the hydrogens on the silicon of the suns.

The alkoxy-substituted hydridosilsesquioxanes provided in the present invention can be easily purified by sublimation, recrystallization and the like. When a mixture is obtained, it can be easily separated and purified by chromatography or the like.

[0012]

EXAMPLES The following will explain the embodiments of the present invention by showing Examples, but the present invention is not limited to the following Examples.

Example 1 Octakis (hydridosilsesquioxane) 212 mg
(0.5 mmol), bis (cyclopentadienyl) titanium dicarbonyl 11.7 mg (0.05 mmo
l) is dissolved in 50 mL of toluene and methanol 0.49 is added.
mL (12 mmol) was added, and the mixture was stirred at room temperature for 23 hours. The solution was analyzed by gas chromatography and only octakis (methoxysilsesquioxane) was produced in 62% yield. Sublimation gave octakis (methoxysilsesquioxane) in 49% yield.

Example 2 12.5 mg (0.05 mmol) of bis (cyclopentadienyl) dichlorotitanium was used as a catalyst, and after dissolving in toluene, a hexane solution of n-butyllithium (1.6
M) 60 μL (0.1 mmol) was added, and the reaction time was 1
Reaction was carried out in the same manner as in Example 1 except that the time was 0 minutes, and octakis (methoxysilsesquioxane) alone was added to
Obtained in% yield.

Example 3 Bis (cyclopentadienyl) dichlorotitanium 6
2.3 mg (0.25 mmol), 0.31 mL (0.5 m) of a hexane solution of n-butyllithium (1.6 M)
mol) and the reaction time was 2 hours, and the reaction was performed in the same manner as in Example 2 to obtain only octakis (methoxysilsesquioxane) in a 22% yield.

Example 4 Octakis (hydridosilsesquioxane) 212 mg
(0.5 mmol), bis (cyclopentadienyl) dimethyl zirconium as a catalyst 10.4 mg (0.05
mmol) in 50 mL of toluene and methanol 1
2 mmol was added and the mixture was stirred at room temperature for 5 hours. After further adding 24 mmol of methanol and stirring at room temperature for 1 hour, 10.4 mg (0.05 mmol) of bis (cyclopentadienyl) dimethylzirconium was added, and the mixture was stirred at room temperature for 1 hour. Only octakis (methoxysilsesquioxane) was obtained in 86% yield.

Example 5 8.5 mg of dicobalt octacarbonyl as a catalyst
(0.025 mmol) and the reaction time was 3 hours. The reaction was performed in the same manner as in Example 1 to obtain octamethoxy (hydridosilsesquioxane) monomethoxy-substituted product 26.
%, And dimethoxy substituted product 6% were obtained.

Example 6 The reaction solution of Example 5 was further added with triphenylphosphine 1
When 3.1 mg (0.05 mmol) was added and the mixture was stirred at room temperature for 3 hours, octakis (hydridosilsesquioxane) monomethoxy-substituted 9%, dimethoxy-substituted 19%, trimethoxy-substituted 21%, tetra- 14% methoxy substitution, 5% pentamethoxy substitution, 3% hexamethoxy substitution, 0.4 heptamethoxy substitution
% Mixture was obtained.

Example 7 8.5 mg of dicobalt octacarbonyl as a catalyst
(0.025 mmol) and triphenylphosphine 1
The reaction was performed in the same manner as in Example 5 except that 3.1 mg (0.05 mmol) of the mixture was used and the reaction time was 4 hours, and only the monomethoxy-substituted octakis (hydridosilsesquioxane) was 22%. Obtained in yield.

Example 8 13 mg (0.025 mmol) of bis (triethylphosphine) dicobalt hexacarbonyl was used as a catalyst,
Octakis (hydridosilsesquioxane) was reacted in the same manner as in Example 5 except that the reaction time was 19 hours.
Monomethoxy-substituted 4%, dimethoxy-substituted 13%,
Substituted trimethoxy 22%, Substituted tetramethoxy 22
%, Pentamethoxy-substituted product 13%, hexamethoxy-substituted product 5%, and heptamethoxy-substituted product 1%.

Example 9 Using 39 mg (0.05 mmol) of bis (triphenylphosphine) carbonylchloroiridium as a catalyst,
After reacting in the same manner as in Example 1 except that the reaction time was 21 hours, the mixture was heated and stirred at 80 ° C. for 1 hour. As a result, octakis (hydridosilsesquioxane) monomethoxy-substituted product 23%, dimethoxy-substituted I got 3% body.
After heating and stirring for further 116 hours, 25 mmol of methanol was further added to this reaction solution, and after heating and stirring for 48 hours, 1% of trimethoxy substitution product of octakis (hydridosilsesquioxane), 8% tetramethoxy substitution product, pentamethoxy substitution A mixture of 13% body, 12% hexamethoxy substitution, 4% heptamethoxy substitution and 0.4% octamethoxy substitution was obtained.

Example 10 Octakis (hydridosilsesquioxane) was reacted in the same manner as in Example 1 except that tris (divinyltetramethyldisiloxane) diplatinum 0.025 mmol was used as the catalyst and the reaction time was 2 hours. ) Monomethoxy substitution product 9%, dimethoxy substitution product 10%, trimethoxy substitution product 24%, tetramethoxy substitution product 12%, pentamethoxy substitution product 7%, hexamethoxy substitution product 3%, heptamethoxy substitution product 0.4% A mixture of octamethoxy-substituted product 0.5% was obtained.

Example 11 Bis (cyclooctadiene) platinum 20.6 m as a catalyst
g (0.05 mmol) was used, and the reaction was performed in the same manner as in Example 1 except that the reaction time was 10 hours, and 9% monomethoxy-substituted octakis (hydridosilsesquioxane), 10% dimethoxy-substituted product, Trimethoxy substitution 2
A mixture of 4%, tetramethoxy-substituted product 16%, pentamethoxy-substituted product 6%, and hexamethoxy-substituted product 6% was obtained.

Example 12 Hydride triphenylphosphine copper hexamer 3 as a catalyst
Using 6.2 mg (0.017 mmol), the reaction time was 2
The reaction was performed in the same manner as in Example 1 except that the time was changed to obtain a monomethoxy-substituted octakis (hydridosilsesquioxane) in a 16% yield.

Example 13 54 mg of m-cresol (0.
5 mmol) and the reaction time was 1 hour at room temperature, and the reaction was carried out in the same manner as in Example 1 to obtain only a 19% yield of octakis (hydridosilsesquioxane) mono (m-methylphenoxy) -substituted product. Got with.

[0026]

INDUSTRIAL APPLICABILITY According to the present invention, various alkoxys of hydridosilsesquioxanes, which are useful as heat-resistant materials and flame-retardant materials, and as raw materials for producing coatings and highly porous ceramics by the sol-gel method, Aralkyloxy or allyloxy substitution can be provided in an easy and safe manner.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References J. Am. Chem. Soc. , Vol. 107, No. 26 (1985) p. 8262- p. 8264 (58) Fields surveyed (Int.Cl. ⁷ , DB name) C07F 7/21 C07F 7/04

Claims (13)

(57) [Claims] 1. A general formula (1): (In the formula, n represents a positive integer of 6 or more.) The hydridosilsesquioxane is reacted with an alcohol, a hydroxyarene, or a mixture thereof in the presence of a transition metal-containing catalyst. Thus, some or all of the hydrogen atoms on the silicon of the hydrido silsesquioxane are RO groups (wherein R represents an alkyl group, an aralkyl group, or an aryl group, and they may be the same or different from each other). The method of alkoxylation, aralkyloxylation, or aryloxylation of hydridosilsesquioxanes, which is changed to. 2. A general formula (1): (In the formula, n represents a positive integer of 6 or more.),
The hydridosilsesquioxane is octakis (hydridosilsesquioxane) (n = 8 in the formula 1), decaquis (hydridosilsesquioxane) (in the formula 1,
n = 10), dodecaquis (hydridosilsesquioxane) (n = 12 in formula 1), tetradecaquis (hydridosilsesquioxane) (n = 1 in formula 1)
4), hexadecakis (hydridosilsesquioxane)
(In the formula 1, n = 16) or octadecakis (hydridosilsesquioxane) (in the formula 1, n =
18) or a mixture of some or all of them. 3. The method according to claim 1, wherein the hydroxyarenes are phenols. 4. The method according to claim 1, wherein the alcohol is benzyl alcohol. 5. The method according to claim 1 or 2, wherein the alcohol is an aliphatic alcohol. 6. The method according to claim 1 or 2, wherein the alcohol is methanol. 7. The method according to any one of claims 1 to 6, wherein the transition metal-containing catalyst is a titanium-containing catalyst. 8. The method according to any one of claims 1 to 6, wherein the transition metal-containing catalyst is a zirconium-containing catalyst. 9. The method according to any one of claims 1 to 6, wherein the transition metal-containing catalyst is a ruthenium-containing catalyst. 10. The method according to any one of claims 1 to 6, wherein the transition metal-containing catalyst is a cobalt-containing catalyst. 11. The method according to any one of claims 1 to 6, wherein the transition metal-containing catalyst is an iridium-containing catalyst. 12. The method according to any one of claims 1 to 6, wherein the transition metal-containing catalyst is a platinum-containing catalyst. 13. The method according to any one of claims 1 to 6, wherein the transition metal-containing catalyst is a copper-containing catalyst.