Patent Grant
9243008
The invention relates to new functionalized unsaturated derivatives of (dimethylvinylgermoxy)heptasubstituted silsesquioxanes and the method of their synthesis.
The purpose of the invention was to synthesize molecules of silsesquioxanes having a (dimethylvinylgermoxyl) substituent substituted with an aryl group.
In the first aspect, the invention relates to new functionalized unsaturated derivatives of cage (dimethylvinylgermoxy)heptasubstituted silsesquioxanes of the general formula 1,
in which:
In the second aspect, the invention relates to the method of synthesis of functionalized unsaturated derivatives of (dimethylvinylgermoxy)heptasubstituted silsesquioxanes containing a vinyl group substituted with an aryl group of the general formula 1,
in which:
in which R are the same and represent:
in which R′ represents:
The catalyst is the compound of the general formula 4,
in which n represents 2 or 3, and when n=3, R″ represents triphenylphosphine; and when n=2, R″ represents tricyclohexylphosphine or triisopropylphosphine.
The catalyst is used in an amount ranging from 1×10−3 to 1×10−1 of Ru per 1 mol of (dimethylyinylgermoxy)heptasubstituted silsesquioxane of the formula 2, whereby it is advantageous to use between 0.5×10−2 and 5×10−2 mol, and the most advantageous amount is 2×10−2 mol.
The reaction is advantageously performed with an addition of a copper(I) or (II) salt as a cocatalyst, particularly a copper(I) salt, most advantageously copper(I) chloride in an amount of 10−1-10 mol of Cu, advantageously 5 mol of Cu per 1 mol of Ru.
The reaction is advantageously carried out in a solvent in an atmosphere of an inert gas in a closed system, whereby it is advantageous to use gas that has been purified of oxygen and moisture. The reactions are carried out at temperatures not exceeding 200° C.
It is necessary to use an excess of olefin in relation to (dimethylvinylgermoxy)heptasubstituted silsesquioxane in order to avoid by-processes. It is advantageous to use an excess of between 1.2 and 3 mol of olefin per 1 mol of (dimethylvinylgermoxy)heptasubstituted silsesquioxane of the formula 1, preferably ca. 1.5.
The reactions are carried out in solvents selected from the group consisting of aromatic organic compounds, advantageously in toluene, xylenes, and most advantageously in toluene.
In the method according to the invention, a reaction vessel is loaded in an atmosphere of an inert gas with an appropriate amount of (dimethylvinylgermoxy)heptasubstituted silsesquioxane, a solvent and alkene. The reaction is carried out at temperatures not lower than 130° C., advantageously above 140° C. Due to the minimum temperature limit the reaction is carried out in solvents with a boiling point above 130° C., and in the case of solvents with lower boiling points it is necessary to use closed systems. It is advantageous to maintain a constant temperature throughout the entire duration of the process. The reaction is carried out over 16-48 hours.
If the reaction is carried out with a cocatalyst, the reagents and the catalyst are the first to be introduced into the system, and only then, after the complete dissolution of the catalyst, the cocatalyst is introduced. The presence of the cocatalyst has a favourable effect on increasing the speed of the reaction and the yield of the obtained product, and on reducing the amount of arising by-products.
Cage (dimethylvinylgermoxy)heptasubstituted silsesquioxanes consist of a silicon-oxygen siloxane core and a dimethylvinylgermoxyl group [OGeMe2(CH═CH2)] bound directly to the silicon atom belonging to the inorganic skeleton.
Functionalized unsaturated derivatives of (dimethylvinylgermoxy)heptasubstituted silsesquioxanes to which the invention relates contain a vinyl group of the dimethylyinylgermoxyl group substituted with different functional groups, which makes the compounds suitable as starting materials for obtaining hybrid materials and as nanofillers in new-generation composite materials. In addition, owing to the presence of the germanium atom in the lateral substituent of the silsesquioxane cage, the compounds exhibit specific optical properties and can have an application for the manufacture of precursors for elements of composite optical materials.
The method according to the invention is presented in examples given below which do not limit the applications of the invention.
The analysis of products was performed with:
Identification data of acquired compounds are listed in Table 1.
A Schlenk flask with a volume of 10 mL, equipped with a magnetic stirrer and a glass stopper was evacuated in a triple vacuum-gas cycle and then charged in an atmosphere of an inert gas with 0.1 g (1.04×10−4 mol) of (dimethylvinylgermoxy)heptaisobutylsilsesquioxane, 2 mL of deoxygenated and dried toluene and 24 μL (2.08×10−4 mol) of styrene. The reaction mixture was heated to the boil while constantly stirring, following which a 0.0015 g (2.08×10−6 mol) portion of [chlorohydridocarbonylbis(tricyclohexylphosphine)ruthenium(II)] was added to it. The reaction mixture was heated at a temperature of 140° C. for 24 hours. The solvent was then evaporated under vacuum, and the residues were combined with 2 mL of methanol. The solvent was decanted, and the remaining precipitate was washed again with 2 mL of methanol. [Dimethyl(E)-styrylgermoxy]heptaisobutylsilsesquioxane in the form of powder was obtained and dried under vacuum (isolation yield of 88%).
Following the procedure set out in Example I, a reaction was carried out between (dimethylvinylgermoxy)heptaisobutylsilsesquioxane (0.1 g, 1.04×10−4 mol), 4-bromostyrene (27 μL, 2.08×10−4 mol), toluene (2 mL) and [chlorohydridocarbonylbis(tricyclohexylphosphine)ruthenium(II)] (0.0015 g, 2.08×10−6 mol). [(E)-4-bromostyryldimethylgermoxy]heptaisobutylsilsesquioxane in the form of powder was obtained with a yield of 85%.
Following the procedure set out in Example I, a reaction was carried out between (dimethylvinylgermoxy)heptaisobutylsilsesquioxane (0.1 g, 1.04×10−4 mol), 4-chlorostyrene (25 μL, 2.08×10−4 mol), toluene (2 mL) and [chlorohydridocarbonylbis(tricyclohexylphosphine)ruthenium(II)] (0.0015 g, 2.08×10−6 mol). [(E)-4-chlorostyryldimethylgermoxy]heptaisobutylsilsesquioxane in the form of powder was obtained with a yield of 81%.
Following the procedure set out in Example I, a reaction was carried out between (dimethylvinylgermoxy)heptaisobutylsilsesquioxane (0.1 g, 1.04×10−4 mol), 4-trifluoromethylstyrene (31 μL, 2.08×10−4 mol), toluene (2 mL) and [chlorohydridocarbonylbis(tricyclohexylphosphine)ruthenium(II)] (0.0015 g, 2.08×10−6 mol). [Dimethyl(E)-4-trifluoromethylstyrylgermoxy]heptaisobutylsilsesquioxane in the form of powder was obtained with a yield of 87%.
1NMR (CDCl3, δ, ppm): 0.59 (s, 6H, —Ge(CH3)2—); 0.59-0.65 (m, 14H, CH2);
13C NMR (CDCl3, δ, ppm): 1.00 (—Ge(CH3)2—); 22.45, 22.53 (CH2); 23.80,
29Si NMR: (CDCl3, δ, ppm): −67.27, −67.90, −108.14
1NMR (CDCl3, δ, ppm): 0.58 (s, 6H, —Ge(CH3)2—); 0.59-0.65 (m, 14H, CH2);
13C NMR (CDCl3, δ, ppm): 1.00 (—Ge(CH3)2—); 22.47, 22.53 (CH2); 23.81,
29Si NMR: (CDCl3, δ, ppm): −67.25, —67.90, −108.04
1NMR (CDCl3, δ, ppm): 0.54 (s, 6H, —Ge(CH3)2—); 0.56-0.69 (m, 14H, CH2);
13C NMR (CDCl3, δ, ppm): 0.96 (—Ge(CH3)2—); 22.41, 22.50 (CH2); 23.77,
29Si NMR: (CDCl3, δ, ppm): −67.27, −67.89, −107.04
1NMR (CDCl3, δ, ppm): 0.58 (s, 6H, —Ge(CH3)2—); 0.59-0.66 (m, 14H, CH2);
13C NMR (CDCl3, δ, ppm): 1.02 (—Ge(CH3)2—), 22.56 (CH2); 23.82,
29Si NMR: (CDCl3, δ, ppm): −67.25, −67.86, −105.55
| Number | Date | Country | Kind |
|---|---|---|---|
| 411196 | Feb 2015 | PL | national |
| Number | Name | Date | Kind |
|---|---|---|---|
| 7662308 | Jeganathan | Feb 2010 | B2 |
| 7947848 | Ohrlein | May 2011 | B2 |
| 8299283 | Chujo | Oct 2012 | B2 |
| 9012673 | Mabry | Apr 2015 | B1 |
| 9018400 | Marciniec | Apr 2015 | B2 |
| 20050215807 | Morimoto | Sep 2005 | A1 |
| 20100222503 | Laine | Sep 2010 | A1 |
| 20130158282 | Christiansen | Jun 2013 | A1 |
| 20140275445 | Yamanaka | Sep 2014 | A1 |
| Entry |
|---|
| Frackowiak et al., Organometallics, vol. 34, No. 16, pp. 3950-3958 (2015). |
