(19)
(11)EP 2 606 054 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
03.10.2018 Bulletin 2018/40

(21)Application number: 11757980.5

(22)Date of filing:  04.08.2011
(51)International Patent Classification (IPC): 
C07F 7/21(2006.01)
(86)International application number:
PCT/PL2011/000084
(87)International publication number:
WO 2012/023867 (23.02.2012 Gazette  2012/08)

(54)

FUNCTIONALIZED POLYHEDRAL OCTAVINYLSILSESQUIOXANES

FUNKTIONALISIERTE POLYHEDRALE OCTAVINYLSILSESQUIOXANES

OCTAVINYLSILSESQUIOXANES POLYHEDRALES FONCTIONALISES


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 20.08.2010 PL 39216610

(43)Date of publication of application:
26.06.2013 Bulletin 2013/26

(73)Proprietor: Adam Mickiewicz University
61-712 Poznan (PL)

(72)Inventors:
  • MARCINIEC, Bogdan
    62-020 Swarzedz (PL)
  • PIETRASZUK, Cezary
    54-242 Wroclaw (PL)
  • MAJCHRZAK, Mariusz
    61-536 Pozna (PL)
  • ZAK, Patrycja
    60-687 Pozna (PL)

(74)Representative: Lisiecki, Wojciech 
Uniwersytet im Adama Mickiewicza ul. Wieniawskiego 1
PL-61 712 Poznan
PL-61 712 Poznan (PL)


(56)References cited: : 
  
  • YOSHITERU KAWAKAMI ET AL: "Hydrogen-Bonding 3D Networks by Polyhedral Organosilanols: Selective Inclusion of Hydrocarbons in Open Frameworks", ORGANOMETALLICS, ACS, WASHINGTON, DC, US, vol. 29, no. 15, 1 July 2010 (2010-07-01), pages 3281-3288, XP009153171, ISSN: 0276-7333, DOI: 10.1021/OM901120M
  • SULAIMAN S ET AL: "Molecules with Perfect Cubic Symmetry as Nanobuilding Blocks for 3-D Assemblies. Elaboration of Octavinylsilsesquioxane. Unusual Luminescence Shifts May Indicate Extended Conjugation Involving the Silsesquioxane Core", CHEMISTRY OF MATERIALS, AMERICAN CHEMICAL SOCIETY, WASHINGTON, US, vol. 20, no. 17, 15 August 2008 (2008-08-15), pages 5563-5573, XP009153167, ISSN: 0897-4756, DOI: 10.1021/CM801017E
  • MEE YOON LO ET AL: "Organic-Inorganic Hybrids Based on Pyrene Functionalized Octavinylsilsesquioxane Cores for Application in OLEDs", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC; US, vol. 129, no. 18, 21 April 2007 (2007-04-21), pages 5808-5809, XP009153165, ISSN: 0002-7863, DOI: 10.1021/JA070471M
  • MEE YOON LO ET AL: "Silsesquioxane-based nanocomposite dendrimers with photo-luminescent and charge transport properties", CHEMICAL RECORD, JOHN WILEY, NEW YORK, NY, US, vol. 6, no. 3, 22 June 2006 (2006-06-22), pages 157-168, XP009153164, ISSN: 1527-8999, DOI: 10.1002/TCR.20080
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description


[0001] This invention relates to new method to obtain the functionalized polyhedral octavinylsilsesquioxanes.

[0002] Functionalized polyhedral octavinylsilsesquioxanes containing an inorganic siloxane skeleton connected with a wide range of functional groups are a convenient starting material for obtaining hybrid materials and are applicable as nanofillers in new-generation composite materials.

[0003] Feher (1) has described functionalization by means of a cross-metathesis reaction catalyzed by molybdenum complexes. Catalysts used in the method are hard to synthesize and sensitive to moisture and atmospheric oxygen, which considerably limits its application.

[0004] The cross-metathesis reaction (2) with the use of ruthenium complexes is very efficient and selective, although the presence of certain types of functionalized olefins prevents its use because of deactivation of the catalyst taking place, therefore, it cannot be used at all times.

[0005] Sellinger (3) described the functionalization of octavinylsilsesquioxanes by means of the Heck coupling reaction catalyzed with palladium complexes, but the reaction is not stereo- or chemoselective.

[0006] It is an objective of the invention to provide new method to obtain the functionalized polyhedral octavinylsilsesquioxanes.

[0007] This invention relates to a method to obtain functionalized polyhedral octavinylsilsesquioxanes having the general formula 1, in which:

R1 denotes:
  • any hetero aryl group; groups comprising coupled aromatic rings,
  • any aryl or heteroaryl group substituted with equalor different substituents selected from the group: aryl, halogen and substituents comprising heteroatoms selected from the group: N, O, S,
by the silylating coupling of octavinylsilsesquioxane having the general formula 3,

with olefins having the general formula 4,

in which R1 is specified above, in the presence of a ruthenium complex catalyst in the presence of copper compounds as co-catalysts.

[0008] Addition of a copper salt as co-catalyst (specifically copper(I) salt, most preferably copper(I) chloride) in the amount of 10-1 - 10 moles of Cu (preferably 5 moles of Cu) per mole of Ru, has a favorable effect on the reaction course.

[0009] The catalyst is usually a compound having the general formula 5

        RuHCl(CO)[P(R4)3]n     (5)

in which R4 denotes:
  • for n=3 denotes triphenylphosphine,
  • for n=2 denotes tricyclohexylphosphine or triisopropylphosphine.


[0010] The catalyst is used in an amount from 1×10-3 to 1×10-1 mole of Ru per 1 mole of vinyl groups in silsesquioxane, preferably from 0.5×10-2 to 2×10-2 and most preferably 1×10-2 mole.

[0011] The reaction is carried out in a solvent under inert gas in an open or closed system and, preferably, the gas is used after any oxygen or moisture has been removed therefrom. In open systems, the reaction is carried out at temperatures not higher than the reaction mixture boiling point. In closed systems, the reactions are carried out at temperatures not higher than 200°C. Preferably, though not necessarily, an excess of olefin relative to the octavinylsilsesquioxane is used, to speed up the reaction. Preferably, the olefin is used in an excess of from 1.1 to 2, most preferably approximately 1.5, moles of olefin per mole of CH2=CH groups in octavinylsilsesquioxane.

[0012] The reaction is carried out in solvents selected from the group comprising: aromatic organic compounds, chlorinated aliphatic compounds, chlorinated aromatic compounds. The reaction is preferably carried out in methylene chloride or toluene.

[0013] In the method of the invention, the reactor is filled under inert gas with a suitable amount of octavinylsilsesquioxane, solvent, and alkene and catalyst and, optionally, co-catalyst, upon which the reaction mixture is stirred and heated, preferably, to a temperature which is optimum for the given system of reagents and solvent. The reaction is continued for 1-48 hours at a temperature in the range 20 - 200°C, preferably, at a temperature in the boiling range of the reaction mixture. The catalyst is preferably added after mixing and heating the other reactants. The co-catalyst is preferably added after the catalyst.

[0014] Preferably, all the reagents are dewatered and deoxidized prior to being reacted.

[0015] In the case of reactions effected in closed systems, the reaction is carried out in the same conditions as in open systems, using higher temperatures for 1-48 hours at temperatures up to 200°C. A raw product is separated from the reaction mixture by precipitation using an appropriate solvent, in which the product will not get dissolved, or by removing the solvent in which the reaction was effected. In the latter case, after evaporating the solvent, the catalyst is removed by eluting with a solvent which dissolves selectively the catalyst alone. Preferably, hexane is used for precipitating the product or eluting the catalyst. A raw product is further purified by known methods, depending on its intended use.

[0016] Application, in the method of the invention, of the silylating coupling process enables the synthesis of functionalized polyhedral silsesquioxanes with high yields and selectivities.

[0017] Modification of polyhedral vinylsilsesquioxanes with suitably designed groups - chromophores with π-coupled systems - enables [them] to be used, for instance, in electrochemistry for polymerization or as materials with controlled fluorescence and photoluminescence, characterized by specific photophysicochemical parameters.

[0018] The method of the invention shall now be illustrated by way of Examples which are not intended to limit the scope of applicability of the invention.

[0019] The product analysis is performed as follows:
  • 1H and 13C-NMR spectra were obtained using the spectrometer Varian Gemini 300, at 300 and 75 MHz
  • 29Si spectra were obtained using the spectrometer Varian Avance 600, at 119, 203 MHz. All NMR measurements were performed after filling the test tubes under argon. Deoxidized and dewatered, deuterated benzene was used as solvent. The measurements were performed at a room temperature.
  • mass spectra: were obtained using 4000 Q TRAP from Applied Biosystems,

Example I



[0020] A 5 mL reactor, equipped with a magnetic stirrer, a reflux condenser with an attachment enabling the reaction system to be connected to a vacuum-and-gas line was filled under inert gas with 0.01 g (1.58×10-5 mol) octavinylsilsesquioxane, followed, in the following order, with 3 mL methylene chloride and 0.019 mL (1.26×10-4 mol) 4-(trifluoromethyl)styrene. The reaction mixture was warmed to 45°C while stirring continuously. Then 0.0009 g (1.26×10-6 mol) [chlorohydridocarbonylbis(tricyclehexylphosphine)ruthenium(II)] was added to the mixture and 5 minutes later 0.0006 g (6.32×10-6 mol) copper(I) chloride was introduced. The reaction mixture was heated for 24 hours at a temperature of 45°C. Then the solvent was subjected to vacuum evaporation and the residue was dissolved in a mixture of hexane and methylene chloride at a ratio by volume of hexane : CH2Cl2 = 10:1 and transferred to a silica-packed chromatographic column to purify the product. This produced octakis[2-(4-trifluoromethylphenyl)ethenyl]octasilsesquioxane in the form of white powder with a yield of 90%. Melting range: 320-324°C.

1H NMR (C6D6, ppm): δ = 6.58 (d, 8H, J = 19.3 Hz, =CHSi), 7.08 (d, 16H, J = 8.5 Hz, C6H4-CF3), 7.22 (d, 16H, J = 8.5 Hz, C6H4-CF3), 7.61 (d, 8H, J = 19.3 Hz, =CH-Ar)

13C NMR (C6D6, ppm): δ = 119.9 (=CHSi), 126.0 (q, CF3), 127.4, 128.1 (C6H4-CF3), 131.4 (q, ipso-C at CF3), 140.1 (ipso-C at C6H4-CF3), 149.2 (=CHAr)

29Si NMR (C6D6, ppm): δ = -78.32

APPI-MS: m/z ([M+H]+, % intensity): 1777 (76), 1778 (100), 1781 (54), 1782 (78), 1784 (54), 1786 (41), 1787 (29)


Example II



[0021] A 5 mL reactor, equipped with a magnetic stirrer, a reflux condenser with an attachment enabling the reaction system to be connected to a vacuum-and-gas line was filled under inert gas with 0.01 g (1.58×10-5 mol) octavinylsilsesquioxane, followed, in the following order, with 3 mL methylene chloride and 0.035 g (1.26×10-4 mol) 4-(9-anthraceneyl)styrene. The reaction mixture was warmed to 45°C while stirring continuously. Then 0.0009 g (1.26×10-6 mol) [chlorohydridocarbonylbis(tricyclehexylphosphine)ruthenium(II)] was added to the mixture and 5 minutes later 0.0006 g (6.32×10-6 mol) copper(I) chloride was introduced. The reaction mixture was heated for 24 hours at a temperature of 45°C. Then the solvent was subjected to vacuum evaporation and the residue was dissolved in a mixture of hexane and methylene chloride at a ratio by volume of hexane : CH2Cl2 = 10:1 and transferred to a silica-packed chromatographic column to purify the product. This produced octakis[2-{4-(9-anthracenyl)phenyl}ethenyl]octasilsesquioxane in the form of a yellow crystalline solid with a yield of 83%. Melting range: 294-298°C.

1H NMR (C6D6, ppm): δ = 6.93 (d, 8H, J = 19.0 Hz, =CHSi), 7.11-7.28 (m, 32H, anthracene), 7.26 (d, 16H, J = 8.2 Hz, -C6H4-), 7.56 (d, 16H, J = 8.2 Hz, -C6H4-), 7.79 (d, 16H, J = 8.5 Hz, anthracene), 7.85 (d, 16H, J = 8.0 Hz, anthracene), 8.09 (d, 8H, J = 19.0 Hz, =CH-Ar), 8.25 (s, 8H, anthracene)

13C NMR (C6D6, ppm): δ = 118.3, 125.4, 125.8, 127.2, 127.3, 127.6, 127.7, 128.7, 130.7, 131.9, 132.0, 136.9, 140.1, 150.2

29Si NMR (C6D6, ppm): δ = -77.99


Example III



[0022] A 5 mL reactor, equipped with a magnetic stirrer, a reflux condenser with an attachment enabling the reaction system to be connected to a vacuum-and-gas line was filled under inert gas with 0.01 g (1.58×10-5 mol) octavinylsilsesquioxane, followed, in the following order, with 3 mL methylene chloride and 0.029 g (1.26×10-4 mol) 4-(1-naphthyl)styrene. The reaction mixture was warmed to 45°C while stirring continuously. Then 0.0009 g (1.26×10-6 mol) [chlorohydridocarbonylbis(tricyclehexylphosphine)ruthenium(II)] was added to the mixture and 5 minutes later 0.0006 g (6.32×10-6 mol) copper(I) chloride was introduced. The reaction mixture was heated for 24 hours at a temperature of 45°C. Then the solvent was subjected to vacuum evaporation and the residue was dissolved in a mixture of hexane and methylene chloride at a ratio by volume of hexane : CH2Cl2 = 10:1 and transferred to a silica-packed chromatographic column to purify the product. This produced octakis[2-{4-(1-naphthyl)phenyl}ethenyl]octasilsesquioxane in the form of opalescent solid with a yield of 93%. Melting range: 318-320 °C.

1H NMR (400 MHz, CDCl3): δ = 6.54 (d, 8H, J = 19.5 Hz, =CHSi), 7.39 - 7.56 (m, 48H, C6H4-C10H7), 7.61 (d, 8H, J = 19.2 Hz, =CH-C6H4-C10H7), 7.72 (d, 16H, J = 13.2, 8.1 Hz, -C6H4-C10H7), 7.85 - 7.95 (m, 16H, =CH- C6H4-C10H7).

13C NMR (75 MHz, CDCl3): δ = 117.5 (=CHSi), 125.9, 125.2, 125.6, 125.8, 126.7, 126.8, 127.6, 128.1, 130.2, 131.3, 133.6, 136.3, 139.5, 141.4, 148.6 (=CH-C6H4-Ph).

29Si NMR (79 MHz, CDCl3): δ = - 77.89.


Example IV



[0023] A 5 mL reactor, equipped with a magnetic stirrer, a reflux condenser with an attachment enabling the reaction system to be connected to a vacuum-and-gas line was filled under inert gas with 0.01 g (1.58×10-5 mol) octavinylsilsesquioxane, followed, in the following order, with 3 mL methylene chloride and 0.029 g (1.26×10-4 mol) 4-(1-naphthyl)styrene. The reaction mixture was warmed to 110°C while stirring continuously. Then 0.0009 g (1.26×10-6 mol) [chlorohydridocarbonylbis(tricyclohexylphosphine)ruthenium(II)] was added to the mixture. The reaction mixture was heated for 24 hours at a temperature of 110°C. Then the solvent was subjected to vacuum evaporation and the residue was dissolved in a mixture of hexane and methylene chloride at a ratio by volume of hexane : CH2Cl2 = 10:1 and transferred to a silica-packed chromatographic column to purify the product. This produced octakis[2-{4-(1-naphthyl)phenyl}ethenyl]octasilsesquioxane in the form of opalescent solid with a yield of 51%. NMR analysis as in Example III.

Example V



[0024] A 5 mL reactor, equipped with a magnetic stirrer, a reflux condenser with an attachment enabling the reaction system to be connected to a vacuum-and-gas line was filled under inert gas with 0.01 g (1.58×10-5 mol) octavinylsilsesquioxane, followed, in the following order, with 3 mL methylene chloride and 0.024 g (1.26×10-4 mol) 4-(1-thienyl)styrene. The reaction mixture was warmed to 45°C while stirring continuously. Then 0.0009 g (1.26×10-6 mol) [chlorohydridocarbonylbis(tricyclohexylphosphine)ruthenium(II)] was added to the mixture and 5 minutes later 0.0006 g (6.32×10-6 mol) copper(I) chloride was introduced. The reaction mixture was heated for 24 hours at a temperature of 45°C. Then the solvent was subjected to vacuum evaporation and the residue was dissolved in a mixture of hexane and methylene chloride at a ratio by volume of hexane : CH2Cl2 = 10:1 and transferred to a silica-packed chromatographic column to purify the product. This produced octakis[2-{4-(1-thienyl)phenyl}ethenyl]octasilsesquioxane in the form of yellowish solid with a yield of 90%. Melting range: 283 - 285°C.

1H NMR (400 MHz, CDCl3): δ = 6.35 (d, 8H, J = 19.2 Hz, =CHSi), 7.26 (d, 8H, J = 3.9 Hz, -C6H4-C4H2S), 7.32 (d, 8H, J = 1.2 Hz, -C6H4-C4H2S), 7.32 (d, 8H, J = 8.3 Hz, -C6H4-), 7.38 (d, 8H, J = 19.1 Hz, =CH-C6H4-), 7.44 - 7.50 (m, 16H, -C6H4-C4H2S), 7.62 (d, 16H, J = 9.6 Hz, -C6H4-).

13C NMR (75 MHz, CDCl3): δ = 117.4 (=CHSi), 123.5, 125.3, 126.2, 127.7, 128.3, 135.2, 136.6, 144.1, 148.7 (=CH-C6H4-Ph).

29Si NMR (79 MHz, CDCl3): δ = - 78.20.


Example VI



[0025] A 5 mL reactor, equipped with a magnetic stirrer, a reflux condenser with an attachment enabling the reaction system to be connected to a vacuum-and-gas line was filled under inert gas with 0.01g (1.58×10-5 mol) octavinylsilsesquioxane, followed, in the following order, with 3 mL methylene chloride and 0.016 mL (1.26×10-4 mol) 4-bromostyrene. The reaction mixture was warmed to 45°C while stirring continuously. Then 0.0009 g (1.26×10-6 mol) [chlorohydridocarbonylbis(tricyclohexylphosphine)ruthenium(II)] was added to the mixture and 5 minutes later 0.0006 g (6.32×10-6 mol) copper(I) chloride was introduced. The reaction mixture was heated for 24 hours at a temperature of 45°C. Then the solvent was subjected to vacuum evaporation and the residue was dissolved in a mixture of hexane and methylene chloride at a ratio by volume of hexane : CH2Cl2 = 10:1 and transferred to a silica-packed chromatographic column to purify the product. This produced octakis[2-(4-bromophenyl)ethenyl]octasilsesquioxane in the form of white powder with a yield of 92%. Melting range: 327-330°C.

1H NMR (C6D6, ppm): δ = 6.44 (d, 8H, J = 19.3 Hz, =CHSi), 6.88 (d, 16H, J = 8.5 Hz, C6H4-Br), 7.12 (d, 16H, J = 8.5 Hz, C6H4-Br), 7.50 (d, 8H, J = 19.3 Hz, =CH-Ar)

13C NMR (C6D6, ppm): δ = 117.7 (=CHSi), 123.5 (ipso-C at Br of C6H4Br), 128.4 (o-C of C6H4Br), 131.9 (m-C of C6H4Br), 135.7 (ipso-C of C6H4Br), 148.9 (=CHAr)

29Si NMR (C6D6, ppm): δ = -78.07

APPI-MS: m/z ([M+H]+, % intensity): 1862 (16), 1867 (19), 1869 (39), 1872 (87), 1873 (90), 1874 (100), 1876 (77), 1877 (52), 1879 (23).


Example VII



[0026] A 5 mL reactor, equipped with a magnetic stirrer, a reflux condenser with an attachment enabling the reaction system to be connected to a vacuum-and-gas line was filled under inert gas with 0.01g (1.58×10-5 mol) octavinylsilsesquioxane, followed, in the following order, with 3 mL toluene and 0.016 mL (1.26×10-4 mol) 4-bromostyrene. The reaction mixture was warmed to 45°C while stirring continuously. Then 0.0009 g (1.26×10-6 mol) [chlorohydridocarbonylbis(tricyclohexylphosphine)ruthenium(II)] was added to the mixture and 5 minutes later 0.0006 g (6.32×10-6 mol) copper(I) chloride was introduced. The reaction mixture was heated for 24 hours at a temperature of 45°C. Then the solvent was subjected to vacuum evaporation and the residue was dissolved in a mixture of hexane and methylene chloride at a ratio by volume of hexane : CH2Cl2 = 10:1 and transferred to a silica-packed chromatographic column to purify the product. This produced octakis[2-(4-bromophenyl)ethenyl]octasilsesquioxane in the form of white powder with a yield of 90%.

Example VIII



[0027] A 5 mL reactor, equipped with a magnetic stirrer, a reflux condenser with an attachment enabling the reaction system to be connected to a vacuum-and-gas line was filled under inert gas with 0.01g (1.58×10-5 mol) octavinylsilsesquioxane, followed, in the following order, with 3 mL chlorobenzene and 0.016 mL (1.26×10-4 mol) 4-bromostyrene. The reaction mixture was warmed to 45°C while stirring continuously. Then 0.0009 g (1.26×10-6 mol) [chlorohydridocarbonylbis(tricyclohexylphosphine)ruthenium(II)] was added to the mixture and 5 minutes later 0.0006 g (6.32×10-6 mol) copper(I) chloride was introduced. The reaction mixture was heated for 24 hours at a temperature of 45°C. Then the solvent was subjected to vacuum evaporation and the residue was dissolved in a mixture of hexane and methylene chloride at a ratio by volume of hexane : CH2Cl2 =10:1 and transferred to a silica-packed chromatographic column to purify the product. This produced octakis[2-(4-bromophenyl)ethenyl]octasilsesquioxane in the form of white powder with a yield of 88%.

Example IX



[0028] A 5 mL reactor, equipped with a magnetic stirrer, a reflux condenser with an attachment enabling the reaction system to be connected to a vacuum-and-gas line was filled under inert gas with 0.01g (1.58×10-5 mol) octavinylsilsesquioxane, followed, in the following order, with 3 mL toluene and 0.016 mL (1.26×10-4 mol) 4-bromostyrene. The reaction mixture was warmed to 45°C while stirring continuously. Then 0.0009 g (1.26×10-6 mol) [chlorohydridocarbonylbis(tricyclohexylphosphine)ruthenium(II)] was added to the mixture. The reaction mixture was heated for 24 hours at a temperature of 110°C. Then the solvent was subjected to vacuum evaporation and the residue was dissolved in hexane and transferred to a silica-packed chromatographic column to purify the product. This produced octakis[2-(4-bromophenyl)ethenyl]octasilsesquioxane in the form of white powder with a yield of 75%.

Example X



[0029] A 5 mL reactor, equipped with a magnetic stirrer, a reflux condenser with an attachment enabling the reaction system to be connected to a vacuum-and-gas line was filled under inert gas with 0.01g (1.58×10-5 mol) octavinylsilsesquioxane, followed, in the following order, with 3 mL toluene and 0.016 mL (1.26×10-4 mol) 4-bromostyrene. The reaction mixture was warmed to 45°C while stirring continuously. Then 0.0012g (1.26×10-6 mol) [chlorohydridocarbonyltris(triphenylphosphine)ruthenium(II)] was added to the mixture and 5 minutes later 0.0006 g (6,31×10-6 mol) copper(I) chloride was introduced. The reaction mixture was heated for 24 hours at a temperature of 45°C. Then the solvent was subjected to vacuum evaporation and the residue was dissolved in a mixture of hexane and methylene chloride at a ratio by volume of hexane : CH2Cl2 = 10:1 and transferred to a silica-packed chromatographic column to purify the product. This produced octakis[2-(4-bromophenyl)ethenyl]octasilsesquioxane in the form of white powder with a yield of 70%.

Example XI



[0030] A 5 mL reactor, equipped with a magnetic stirrer, a reflux condenser with an attachment enabling the reaction system to be connected to a vacuum-and-gas line was filled under inert gas with 0.01g (1.58×10-5 mol) octavinylsilsesquioxane, followed, in the following order, with 3 mL toluene and 0.016 mL (1.26×10-4 mol) 4-bromostyrene. The reaction mixture was warmed to 110°C while stirring continuously. Then 0.0009 g (1.26×10-6 mol) [chlorohydridocarbonylbis(tricyclohexylphosphine)ruthenium(II)] was added to the mixture. The reaction mixture was heated for 24 hours at a temperature of 110°C. Then the solvent was subjected to vacuum evaporation and the residue was dissolved in a mixture of hexane and methylene chloride at a ratio by volume of hexane : CH2Cl2 = 10:1 and transferred to a silica-packed chromatographic column to purify the product. This produced octakis[2-(4-bromophenyl)ethenyl]-octasilsesquioxane in the form of white powder with a yield of 52%.

Example XII



[0031] A 5 mL reactor, equipped with a magnetic stirrer, a reflux condenser with an attachment enabling the reaction system to be connected to a vacuum-and-gas line was filled under inert gas with 0.01 g (1.58×10-5 mol) octavinylsilsesquioxane, followed, in the following order, with 3 mL methylene chloride and 0.015 mL (1.26×10-4 mol) 4-chlorostyrene. The reaction mixture was warmed to 45°C while stirring continuously. Then 0.0009 g (1.26×10-6 mol) [chlorohydridocarbonylbis(tricyclohexylphosphine)ruthenium(II)] was added to the mixture and 5 minutes later 0.0006 g (6.32×10-6 mol) copper(I) chloride was introduced. The reaction mixture was heated for 24 hours at a temperature of 45°C. Then the solvent was subjected to vacuum evaporation and the residue was dissolved in a mixture of hexane and methylene chloride at a ratio by volume of hexane : CH2Cl2 = 10:1 and transferred to a silica-packed chromatographic column to purify the product. This produced octakis[2-(4-chlorophenyl)ethenyl]octasilsesquioxane in the form of white powder with a yield of 94%. Melting range: 300-302°C.

1H NMR (C6D6, ppm): δ = 6.44 (d, 8H, J = 19.0 Hz, =CHSi), 6.97 (s, 32H, C6H4-Cl), 7.53 (d, 8H, J = 19.0 Hz, =CH-Ar)

13C NMR (C6D6, ppm): δ = 117.9 (=CHSi), 128.5 (o-C of C6H4Cl), 129.2 (m-C of C6H4Cl), 135.5 (ipso-C at Cl of C6H4Cl), 135.7 (ipso-C of C6H4Cl), 149.1 (=CHAr)

29Si NMR (C6D6, ppm): δ = -78.06

APPI-MS: m/z ([M+H]+, % intensity): 1512 (23), 1513 (26), 1514 (57), 1515 (79), 1516 (92), 1517 (95), 1518 (100), 1520 (80), 1521 (65), 1522 (46), 1523 (32), 1524 (20), 1525 (13)


Example XIII



[0032] A 5 mL reactor, equipped with a magnetic stirrer, a reflux condenser with an attachment enabling the reaction system to be connected to a vacuum-and-gas line was filled under inert gas with 0.01 g (1.58×10-5 mol) octavinylsilsesquioxane, followed, in the following order, with 3 mL methylene chloride and 0.023 g (1.26×10-4 mol) 4-vinylbiphenyl. The reaction mixture was warmed to 45°C while stirring continuously. Then 0.0009 g (1.26×10-6 mol) [chlorohydridocarbonylbis(tricyclohexylphosphine)ruthenium(II)] was added to the mixture and 5 minutes later 0.0006 g (6.32x10-6 mol) copper(I) chloride was introduced. The reaction mixture was heated for 24 hours at a temperature of 45°C. Then the solvent was subjected to vacuum evaporation and the residue was dissolved in a mixture of hexane and methylene chloride at a ratio by volume of hexane : CH2Cl2 = 10:1 and transferred to a silica-packed chromatographic column to purify the product. This produced octakis[2-(4-biphenyl)ethenyl]octasilsesquioxane in the form of white powder with a yield of 83%. Melting range: 280-285°C.

1H NMR (C6D6, ppm): δ = 6.75 (d, 8H, J = 19.3 Hz, =CHSi), 7.09 -7.22 (m, 32H, C6H4-Ph), 7.34 - 7.46 (m, 40H, =CH-C6H4-C6H5), 7.91 (d, 8H, J = 19.3 Hz, =CH-C6H4-Ph)

13C NMR (C6D6, ppm): = 117.7 (=CHSi), 127.3, 127.4, 128.0, 129.0, 129.1, 136.7, 141.0, 142.3, 150.0 (=CH-C6H4-Ph)

29Si NMR (C6D6, ppm): δ = -77.71

APPI-MS: m/z ([M+H]+, % intensity): 1848 (14), 1849 (67), 1850 (100), 1851 (99), 1852 (75), 1853 (49), 1854 (24), 1855 (14), 1856 (9).


Literature:



[0033] 

1. Feher, F.J.; Soulivong, D.; Eklund, A.G.; Wydham, K.D. Chem. Commun. 1997, 1185.

2. Itami, Y.; Marciniec, B.; Kubicki, M. Chem. Eur. J. 2004, 10, 1239.

3. Sellinger (3) Sellinger, A.; Tamaki, R.; Laine, R. M.; Ueno, K.; Tanabe, H.; Williams, E.; Jabbourd, G. E. Chem. Commun. 2005, 3700.




Claims

1. A method to obtain functionalized polyhedral octavinylsilsesquioxanes having the general formula 1 in which:

R1 denotes:

• any hetero aryl group; groups comprising coupled aromatic rings,

• any aryl or heteroaryl group substituted with equal or different substituents, selected from the group: aryl, halogen and substituents comprising heteroatoms selected from the group: N, O, S,

by the silylating coupling of octavinylsilsesquioxane having the general formula 3,

with olefins having the general formula 4,

in which R1 is specified above, in the presence of a ruthenium complex catalyst having the general formula 5

        RuHCl(CO)[P(R4)3]n     (5)

in which R4:

for n=3 denotes triphenylphosphine,

for n=2 denotes tricyclohexylphosphine or triisopropylphosphine,

in which a copper compound is used as a co-catalyst.
 
2. A method as claimed in claim 1 wherein the co-catalyst is used in the amount of 10-1 - 10 moles of Cu per mole of Ru.
 
3. A method as claimed in claim 2 wherein the co-catalyst is used in the amount of 5 moles of Cu per mole of Ru.
 
4. A method as claimed in claim 2 or 3 wherein copper(I) salts are used as co-catalyst.
 
5. A method as claimed in claim 4wherein copper(I) chloride is used as co-catalyst.
 


Ansprüche

1. Verfahren zur Gewinnung von funktionalisierten Käfig-Octavinylsilsesquioxane mit der allgemeinen Formel 1, in der:

R1 bezeichnet:

• eine beliebige Heteroarylgruppe; Gruppen die gekoppelte aromatische Ringe enthalten,

• eine beliebige Aryl- oder Heteroaryl-Gruppe, substituiert mit gleichen oder verschiedenen Substituenten, ausgewählt aus der Gruppe: Aryl, Halogen, sowie Substituenten, die Heteroatome enthalten, ausgewählt aus der Gruppe: N, O, S

beruhend auf der Reaktion der silylierenden Kopplung von Octavinylsilsesquioxane mit der allgemeinen Formel 3,

mit Olefinen mit der allgemeinen Formel 4,

in R1 wie weiter oben genannte Bedeutung hat, in der Anwesenheit des Ruthenkomplexes als Katalysator mit der allgemeinen Formel 5

        RuHCl(CO)[P(R4)3]n     (5)

wobei R4 :

für n=3 Triphenylphosphan bedeutet,

für n=2 Tricyclohexylphosphan lub Triisopropylphosphan bedeutet

in Anwesenheit einer Kupferverbindung als Cokatalysator.
 
2. Verfahren nach Anspruch 1 gekennzeichnet dadurch, dass der Cokatalysator in einer Menge von 10-1 - 10 Mol Cu pro Mol Ru angewandt wird.
 
3. Verfahren nach Anspruch 2 gekennzeichnet dadurch, dass der Cokatalysator in einer Menge von 5 Mol Cu pro Ru angewandt wird.
 
4. Verfahren nach Anspruch 1 oder 2 gekennzeichnet dadurch, dass als Cokatalysator Kupfersalze(I) eingesetzt werden.
 
5. Verfahren nach Anspruch 4, gekennzeichnet dadurch, dass als Cokatalysator Kupferchlorid(I) eingesetzt wird.
 


Revendications

1. Le procédé d'obtention des octavinylsilsesquioxanes fonctionnalisés, de type cage, ayant la formule générale 1, où

R1 désigne:

• tout groupe hétéroaryle; les groupes contenant des cycles aromatiques couplés,

• tout groupe aryle ou hétéroaryle, substitué par des substituants égaux ou différents, choisis dans le groupe: aryle, halogène et substituants contenant des hétéroatomes choisis dans le groupe: N, O, S

basé sur la réaction de couplage silylant de l'octavinylsilsesquioxane, ayant la formule générale 3,

avec des oléfines, ayant la formule générale 4,

où R1 a la désignation indiquée ci-dessus, en présence du complexe de ruthénium en tant que catalyseur, ayant la formule générale 5

        RuHCl(CO)[P(R4)3]n     (5)

où R4 :

dans le cas de n=3 désigne la triphénylphosphine,

dans le cas de n=2 désigne la tricyclohexylphosphine ou la triisopropylphosphine

en présence d'un composé de cuivre en tant que cocatalyseur.
 
2. Le procédé, selon la revendication 1, caractérisé en ce que, le cocatalyseur est utilisé en une quantité de 10-1 - 10 moles de Cu par une mole de Ru.
 
3. Le procédé, selon la revendication 2, caractérisé en ce que, le cocatalyseur est utilisé en une quantité de 5 moles de Cu par une mole de Ru.
 
4. Le procédé, selon la revendication 1 ou 2, caractérisé en ce que ce sont des sels de cuivre(I) qui sont utilisés en tant que cocatalisateur.
 
5. Le procédé, selon la revendication 4, caractérisé en ce que c'est le chlorure de cuivre(I) qui est utilisé en tant que cocatalisateur.
 






Cited references

REFERENCES CITED IN THE DESCRIPTION



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Non-patent literature cited in the description