Patent Grant
9150596
The subject of invention are new functionalized unsaturated double-decker derivatives of divinylsilsesquioxanes.
The structure of double-decker divinyl-substituted silsesquioxanes is different from that of the symmetric system of cubic cages described by the formula (RSiO3/2)n n=8 (T8) and includes two cyclosiloxane rings in parallel planes with 8 inert R1 groups at the silicon atoms of each ring. The rings are joined by bridges of two types: the first type joins the opposite oxygen atoms, while the second type is via O2SiCH═CH2 groups. In this structure the vinyl groups at the silicon atoms are at the two opposite sides of the molecule and decide about its asymmetry relative to R3 groups at the silicon atoms of siloxane rings (WO2003/024870).
Double-decker functionalized unsaturated derivatives of divinylsilsesquioxanes, built of an inorganic siloxane skeleton that can bind a wide range of functional groups, make suitable substrate for the synthesis of hybrid materials and can be used as nanofillers in the new generation composite materials. The presence of unsaturated carbon-carbon bonds additionally improves the photophysical properties of these compounds. Miyashita has described carbazole silsesquioxane derivatives and their interesting optoelectronic properties that permit their use as organic electroluminescence diodes (M. Kohri, J. Matusi, A. Watanabe, T. Miyashita Chem. Lett. 2010, 39, 1162). Lee has presented the use of silsesquioxane derivatives as ligands for the synthesis of titanium coordination compounds that represent the group of metallasilsesquioxane coordination oligomers (M. T. Hay, B. Seurer, D. Holmes, A. Lee Macromolecules 2010, 43, 2108), while Basset has reported their use in the synthesis of zirconium and hafnium complexes used as models of catalysts for polymerisation of olefins immobilised on silica (J. Espinas, J. D. A. Pelletier, E. Abou-Hamad, L. Emsley, J.-M. Basset Organometallics 2012, 31, 7610). The unsaturated amine and norbornene derivatives of silesquioxanes described by Kakimoto have been used for modification of polyimides; when built in the main polymer chain they considerably improved its thermal and optical properties (S. Wu, T. Hayakawa, M. Kakimoto, H. Oikawa Macromolecules 2008, 41).
The known method for the synthesis of double-decker divinylsilsesquioxanes has been presented in patent EP.1428795 and involves the condensation of vinyldichloromethylsilane with a silane derivative of silsesquioxane comprising four reactive Si—OH groups. In this method it is necessary to use chlorosilane susceptible to hydrolysis in the presence of trace amounts of moisture, which interferes with the synthesis and isolation of the product desired. Seurer, B.; Vij, V.; Haddad, T.; Mabry, J. M.; Lee, A. Macromolecules 2010, 43, 9337-9347) have revealed the aryl derivatives of silsesquioxanes containing unsaturated bonds, but these bonds are at the external ends of aryl substituents.
Another known method for functionalization of vinylsilsesquioxanes has been revealed in the Polish patent application P. 392166. This method is based on silylative coupling of monovinyl- and octavinyl-substituted silsesquioxanes with olefins in the presence of ruthenium catalyst. The substrates to the above reactions are symmetric silsesquioxane systems (T8, so of the core Si8O8) with a single reactive vinyl group or with eight vinyl substituents. The silylative coupling reaction leads to mono- or octa-alkenyl substituted products set on a symmetric silsesquioxane core.
The subject of the invention are new functionalized unsaturated double-decker derivatives of divinylsilsesquioxanes, of the general formula 1,
In which
The synthesis of functionalized unsaturated double-decker derivatives of divinylsilsesquioxanes of formula 1,
in which R1, R2 and R3 are as defined above, is based on silylative coupling of the double-decker divinylsilsesquioxanes of the general formula 3,
in which R1 and R2 are as defined above, with olefins of the general formula 4,
in which R3 is as defined above, in the presence of a ruthenium complex as a catalyst. The ruthenium complex used as a catalyst has a general formula 5
RuHCl(CO)[P(R5)3]n (5)
In which n stands for 2 or 3; if n=3, then R5 stands for triphenylphosphine, while if n=2, then R5 stands for tricyclohexylphosphine or triisopropylphosphine.
The catalyst is used in the amount from 1×10−3 to 1×10−1 mole Ru per each mole of the unsaturated group taking part in the reaction of divinylsilsesquioxane of the general formula 3 with an olefin of the general formula 4; it is favourable to use the catalyst in the amount from 0.5×10−2 to 2×10−2 and the most favourable to use 1×10−2 mole. A favourable effect on the course of the reaction has an addition of copper(I) or copper(II) salts as co-catalyst, in particular copper(I) salt, and the most favourable effect has the use of copper(I) chloride in the amount of 10−1-10 Cu mole, favourably 5 Cu moles per 1 Ru mole.
The reaction is performed in a solvent, under neutral gas atmosphere, in an open or closed system, it is favourable to use gas without oxygen and moisture. In open systems the reaction is performed at a temperature not higher than the boiling point of the reaction mixture. In closed systems the reaction is performed at temperatures not higher than 200° C. It is favourable, but not necessary, to use an excess of olefin with respect to divinylsilsesquioxane to hasten the reaction. It is favourable to use olefin in excess of 1.1 to 2 moles per each mole of CH2═CH groups in divinylsilsesquioxane of formula 3, the most favourable excess of olefin in close to 1.5.
The reaction is performed in a solvent chosen from among: aromatic organic compounds, favourably in toluene, benzene, xylenes, the most favourably in toluene; chlorinated aliphatic compounds or their mixtures. It is favourable to perform the reaction in 1,2-dichloroethane, chloroform, methyl chloride; the most favourable is to use methylene chloride or toluene. It is favourable to perform the reaction in the following way. Proper amounts of divinylsilsesquioxane solvent, alkene and catalyst are placed in a reactor under neutral gas atmosphere. The reaction mixture is stirred upon heating up to 40° C. or higher temperature, and the process is continued at a temperature from 40° C. to the boiling point of the reaction mixture. It is favourable to maintain a constant temperature throughout the process. The reaction takes from 1 to 48 hours.
If a co-catalyst is used, it is introduced to the mixture of reagents and a catalyst after having heated it to a temperature above 40° C. The temperature at which the co-catalyst is introduced must be not lower than 40° C. but not higher than the boiling point of the reaction mixture. The presence of the co-catalyst enhances the rate of the reaction and the yield of the product, and reduces the amount of side products formed. It is favourable to have all the reagents dried and deoxygenated prior to the reaction. The reaction in closed systems is performed in the same conditions and in the open systems.
The raw product is isolated from the reaction mixture by precipitation initiated by a solvent chosen from the groups of aliphatic hydrocarbons containing carbon atoms from C5 to C10, MeOH, MeCN, the most favourable is hexane, or by solvent removal. If the second procedure is used, after evaporation of the solvent, the catalyst is washed out by a solvent which is an aliphatic hydrocarbon containing carbon atoms from C5 to C10, which selectively dissolves only the catalyst. The raw product can be subjected to further purification on a chromatographic column with the eluent made of a mixture of aliphatic hydrocarbon and a chloroderivative of an aliphatic hydrocarbon; it is favourable to use hexane:methylene chloride at a ratio from the range 10-0:0-10, the most favourably at the ratio 5:5. After purification the eluent is evaporated and pure product is obtained.
The synthesis of double-decker derivatives of divinylsilsesquioxanes according to the invention is illustrated by the examples given below.
The products were analysed by taking the following spectra:
A reactor of 5 mL in capacity, equipped with a magnetic stirrer, reflux condenser and a cap permitting connection of the reaction system to the vacuum-gas line, was charged under argon atmosphere, with 0.1 g of (8.29×10−5 mol) di[9,19-methylvinyl]-1,3,5,7,11,13,15,17 octa(phenyl)pentacyclo[11.7.1.13,11.15,17.17,15]decasiloxane (DDSQ-Me) and then, subsequently with 2 mL of methylene chloride and 17×10−3 g (1.66×10−4 mole) styrene. The reaction mixture was heated to 45° C. under continuous stirring. Then, 0.0012 g (1.66×10−6 mole) of carbonylchlorohydridebis(tricyclohexylphosphine)ruthenium(II) was added and after 5 minutes a portion of 0.0008 g (8.29×10−6 mole) of copper(I) chloride was added. The reaction mixture was heated for 18 hours at 45° C. Then, the solvent was evaporated under vacuum and 2 mL of n-hexane was added to wash out the catalyst. After filtration, the precipitate was dissolved in a mixture of hexane:methylene chloride at the volume ratio 1:2 and deposited on a chromatographic column filled with silica in order to remove the traces of catalyst left from the product. The product was obtained in the form of white powder in the yield of 95%.
In the same way as described in example I, a reaction was performed between 0.1 g (8.29×10−5 mole) of divinylsilsesquioxane (DDSQ-Me) and 31×10−3 g (1.66×10−4 mole) of 4-bromostyrene, in the presence of 0.0012 g (1.66×10−6 mole) of carbonylchlorohydridebis(tricyclohexylphosphine)ruthenium(II) and 0.0008 g (8.29×10−6 mole) copper(I) chloride. The product was obtained in the form of white powder in the yield of 93%.
In the same way as described in example I, a reaction was performed between 0.15 g (1.24×10−4 mole) of divinylsilsesquioxane (DDSQ-Me) and 35×10−3 g (2.49×10−4 mole) of 4-chlorostyrene in the presence of 0.0018 g (2.49×10−6 mole) of carbonylchlorohydridebis(tricyclohexylphosphine)ruthenium(II) and 0.0012 g (1.24×10−5 mole) copper(I) chloride. The product was obtained in the form of white powder in the yield of 94%.
In the same way as described in example I, a reaction was performed between 0.12 g (9.95×10−5 mole) of divinylsilsesquioxane (DDSQ-Me) and 27×10−3 g (1.99×10−4 mole) of 4-methoxystyrene in the presence of 0.0014 g (1.99×10−6 mole) of carbonylchlorohydridebis(tricyclohexylphosphine)ruthenium(II) and 0.0010 g (9.95×10−6 mole) of copper(I) chloride. The product was obtained in the form of white powder in the yield of 91%.
In the same way as in example I, a reaction was performed between 0.1 g (8.29×10−5 mole) of divinylsilsesquioxane (DDSQ-Me) and 28×10−3 g (1.66×10−4 mol) of 4-(trifluormethyl)styrene in the presence of 0.0012 g (1.66×10−6 mole) of carbonylchlorohydridebis(tricyclohexylphosphine)ruthenium(II) and 0.0008 g (8.29×10−6 mole) copper(I) chloride. The product was obtained in the form of white powder in the yield of 90%.
In the same way as described in example I, a reaction was performed between 0.1 g (7.52×10−5 mole) of di[9.19-phenylvinyl]-1,3,5,7,11,13,15,17 octa(phenyl)pentacyclo[11.7.1.13,11.15,17.17,15]decasiloxane (DDSQ-Ph) and 15×10−3 g (1.50×10−4 mole) of styrene in the presence of 0.0011 g (1.50×10−6 mole) of carbonylchlorohydridebis(tricyclohexylphosphine)ruthenium(II) and 0.0007 g (7.52×10−6 mole) of copper(I) chloride. The product was obtained in the form of white powder in the yield of 903%.
In the same way as described in example I, a reaction was performed between 0.14 g (1.05×10−4 mole) divinylsilsesquioxane (DDSQ-Ph) and 36×10−3 g (2.10×10−4 mole) 4-(trifluormethyl)styrene in the presence of 0.0015 g (2.10×10−6 mole) carbonylchlorohydridebis(tricyclohexylphosphine)ruthenium(II) and 0.0010 g (1.05×10−5 mole) of copper(I) chloride. The product was obtained in the form of white powder in the yield of 88%.
In the same way as described in example I, a reaction was performed between 0.11 g (8.27×10−5 mole) of divinylsilsesquioxane (DDSQ-Ph) and 20×10−3 g (1.65×10−4 mole) 4-methylstyrene in the presence of 0.0012 g (1.65×10−6 mol) carbonylchlorohydridebis(tricyclohexylphosphine)ruthenium(II) and 0.0008 g (8.27×10−6 mole) of copper(I) chloride. The product was obtained in the form of white powder in the yield of 91%.
In the same way as described in example I, a reaction was performed between 0.1 g (7.52×10−5 mole) of divinylsilsesquioxane (DDSQ-Ph) and 28×10−3 g (1.50×10−4 mole) of 4-bromostyrene in the presence of 0.0011 g (1.50×10−6 mole) carbonylchlorohydridebis(tricyclohexylphosphine)ruthenium(II) and 0.0007 g (7.52×10−6 mole) copper(I) chloride. The product was obtained in the form of white powder in the yield of 95%.
In the same way as described in example I, a reaction was performed between 0.14 g (1.05×10−4 mole) of divinylsilsesquioxane (DDSQ-Ph) and 29×10−3 g (2.10×10−4 mol) of 4-chlorostyrene in the presence of 0.0015 g (2.10×10−6 mole) carbonylchlorohydridebis(tricyclohexylphosphine)ruthenium(II) and 0.0010 g (1.05×10−5 mole) copper(I) chloride. The product was obtained in the form of white powder in the yield of 91%.
In the same way as described in example I, a reaction was performed between 0.1 g (7.19×10−5 mol) di[9,19-(4-methoxyphenyl)vinyl]-1,3,5,7,11,13,15,17 octa(phenyl)pentacylo[11.7.1.13,11.15,17.17,15]deca-siloxane (DDSQ-4-MeOPh) and 14.5×10−3 g (1.44×10−4 mole) styrene in the presence of 0.0010 g (1.44×10−6 mole) of carbonylchlorohydridebis(tricyclohexylphosphine)ruthenium(II) and 0.0007 g (7.19×10−6 mole) of copper(I) chloride. The product was obtained in the form of white powder in the yield of 87%.
In the same way as described in example I, a reaction was performed between 0.12 g (8.63×10−5 mole) of divinylsilsesquioxane (DDSQ-4-MeOPh) and 31.5×10−3 g (1.72×10−4 mole) of 4-bromostyrene in the presence of 0.0012 g (1.72×10−6 mole) of carbonylchlorohydridebis(tricyclohexylphosphine)ruthenium(II) and 0.0008 g (8.63×10−6 mole) of copper(I) chloride. The product was obtained in the form of white powder in the yield of 85%.
In the same way as described in example I, a reaction was performed between 0.1 g (7.19×10−5 mole) of divinylsilsesquioxane (DDSQ-4-MeOPh) and 19.6×10−3 g (1.44×10−4 mole) of 4-chlorostyrene in the presence of 0.0010 g (1.44×10−6 mole) carbonylchlorohydridebis(tricyclohexylphosphine)ruthenium(II) and 0.0007 g (7.19×10−6 mole) of copper(I) chloride. The product was obtained in the form of white powder in the yield of 90%.
1H NMR (CDCl3, δ, ppm): 0.439-0.445 (overlapping s, 6H, CH3; cis and trans
13C NMR (CDCl3, δ, ppm): −0.79, 123.94, 126.78, 127.52 (t, J = 7.9 Hz), 127.77,
29Si NMR (CDCl3, δ, ppm): −30.17 (cis, trans), −78.30 (cis, trans), −79.15 (cis),
1H NMR (CDCl3, δ, ppm): 0.439-0.445 (overlapping s, 6H, CH3; cis and trans
13C NMR (CDCl3, δ, ppm): −0.83, 122.27 (d, J = 1.0 Hz), 124.93, 127.57
29Si NMR (CDCl3, δ, ppm): −30.46 (cis, trans), −78.27 (cis, trans), −79.31 (cis),
1H NMR (CDCl3, δ, ppm): 0.430-0.431 (overlapping s, 6H, CH3, cis and trans
13C NMR (CDCl3, δ, ppm): −0.83, 124.77, 127.57 (t, J = 5.9 Hz), 127.81, 127.94,
29Si NMR (CDCl3, δ, ppm): −30.44 (cis, trans), −78.28 (cis, trans), −79.30 (cis),
1H NMR (CDCl3, δ, ppm): 0.43-0.44 (overlapping s, 6H, CH3, cis and trans
13C NMR (CDCl3, δ, ppm): −0.76, 21.26, 122.64, 126.74, 127.52 (t, J = 6.1 Hz),
29Si NMR (CDCl3, δ, ppm): −29.93 (cis, trans), −78.30 (cis, trans), −79.16 (cis),
1H NMR (CDCl3, δ, ppm): 0.46-0.47 (overlapping s, 6H, CH3, cis and trans
13C NMR (CDCl3, δ, ppm): −0.83, 123.03 (d, J = 1.7 Hz), 125.31 (q, CF3), 126.86,
29Si NMR (CDCl3, δ, ppm): −36.00 (cis, trans), −83.42 (cis, trans), −84.54 (cis),
1H NMR (CDCl3, δ, ppm): 6.56 (d, 2H, JHH = 19.2 Hz, ═CH—Si, cis and trans
13C NMR (CDCl3, δ, ppm): 122.26, 126.9, 127.44 (t, J = 7.6 Hz), 127.8, 128.37,
29Si NMR (CDCl3, δ, ppm): −45.07 (cis, trans), −77.97 (cis, trans), −79.24 (cis),
1H NMR (CDCl3, δ, ppm): 6.63 (d, 2H, JHH = 19.2 Hz, ═CH—Si), 7.12 (d, 2H, JHH =
13C NMR (CDCl3, δ, ppm): 125.16, 125.25, 125.32 (q, CF3), 125.78 (d, J = 2.0
29Si NMR (CDCl3, δ, ppm): −45.21 (cis, trans), −77.87 (cis, trans), −79.35 (cis),
1H NMR (CDCl3, δ, ppm): 2.34 (br s, 6H, CH3, cis and trans mixture), 6.51 (d,
13C NMR (CDCl3, δ, ppm): 120.94, 126.87, 127.45 (t, J = 9.6 Hz), 127.79,
29Si NMR (CDCl3, δ, ppm): −49.46 (cis, trans), −83.21 (cis, trans), −84.49 (cis),
1H NMR (CDCl3, δ, ppm): 6.43 (d, 2H, JHH = 19.2 Hz, ═CH—Si), 6.96 (d, 2H, JHH =
13C NMR (CDCl3, δ, ppm): 122.46 (d, J = 3.1 Hz), 123.4, 127.5 (t, J = 12.2 Hz),
29Si NMR (CDCl3, δ, ppm): −50.02(cis, trans), −83.12 (cis, trans), −84.58 (cis),
1H NMR (CDCl3, δ, ppm): 6.51 (d, 2H, JHH = 19.2 Hz, ═CH—Si), 7.07 (d, 2H, JHH =
13C NMR (CDCl3, δ, ppm): 123.2, 127.48 (t, J = 9.3 Hz), 127.82, 127.86, 128.05,
29Si NMR (CDCl3, δ, ppm): −44.81(cis, trans), −77.93 (cis, trans), −79.38 (cis),
1H NMR (CDCl3, δ, ppm): 3.79 (br s, 6H, OCH3, cis and trans mixture), 6.58 (d,
13C NMR (CDCl3, δ, ppm): 54.94, 113.55, 122.7, 125.72, 126.89, 127.42 (t, J =
29Si NMR (CDCl3, δ, ppm): −49.04 (cis, trans), −83.26 (cis, trans), −84.55 (cis),
1H NMR (CDCl3, δ, ppm): 3.78-3.79 (overlapping s, 6H, OCH3, cis and trans
13C NMR (CDCl3, δ, ppm): 54.96, 113.61, 122.39 (d, J = 3.2 Hz), 123.82 (d, J =
29Si NMR (CDCl3, δ, ppm): −44.14 (cis, trans), −78.02 (cis, trans), −79.49 (br s, cis,
1H NMR (CDCl3, δ, ppm): 3.77-3.78 (overlapping s, 6H, OCH3, cis and trans
13C NMR (CDCl3, δ, ppm): 54.97, 113.61, 123.63 (d, J = 2.3 Hz), 125.41 (d, J =
29Si NMR (CDCl3, δ, ppm): −49.34 (cis, trans), −83.24 (cis, trans), −84.71 (br s, cis,
| Number | Date | Country | Kind |
|---|---|---|---|
| 407444 | Mar 2014 | PL | national |
| Number | Name | Date | Kind |
|---|---|---|---|
| 20040249103 | Morimoto et al. | Dec 2004 | A1 |
| 20050009982 | Inagaki et al. | Jan 2005 | A1 |
| Number | Date | Country |
|---|---|---|
| 1428795 | Jun 2004 | EP |
| 1686133 | Aug 2006 | EP |
| 03024870 | Mar 2003 | WO |
| Entry |
|---|
| Translation of Polish Patent Application No. 392166 filed Aug. 20, 2010. |
| Kohri et al; “Synthesis and optoelectronic properties of completely carbazole-substituted double-decker-shaped silsesquioxan;.” Chem. Lett., 2010, vol. 39; Oct. 5, 2010; pp. 1162-1163. |
| Espinas et al; “A Silica-supported double-decker silsesquioxane provides a second skin for the selective generation of bipodal surface organometallic complexes;” Organometallics, 2012, vol. 31; Oct. 23, 2012; pp. 7610-7617. |
| Seurer et al; “Thermal transitions and reaction kinetics of polyhedral silsesquioxane containing phenylethynylphthalimides;” Macromolecules, 2010, vol. 43; Oct. 19, 2010; pp. 9337-9347. |
| Hay et al; “A novel linear titanium (IV)-POSS coordination polymer,” Macromolecules, 2010, vol. 43; Feb. 9, 2010; pp. 2108-2110. |
| Wu et al; “Synthesis and characterization of organosoluble aromatic polyimides containing POSS in main chain derived from double-decker-shaped silsesquioxane;” Macromolecules, 2008, vol. 41; Apr. 25, 2008; pp. 3481-3487. |
| Number | Date | Country | |
|---|---|---|---|
| 20150252064 A1 | Sep 2015 | US |
