83% |
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Example XIIA 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) <strong>[69655-76-1]octavinylsilsesquioxane</strong>, 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 (1.26x 10"6 mol) [chlorohydridocarbonylbis(tricyclohexyl- phosphine)ruthenium(II)] was added to the mixture and 5 minutes later 0.0006 g (6.32x 10"6 mol) copper(I) chloride was introduced. The reaction mixture was heated for24 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 : CH2C12 = 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 94percent. Melting range: 300-302°C.lH NMR (C6D6, ppm): delta = 6.44 (d, 8H, J = 19.0 Hz, =CHSi), 6.97 (s, 32H, C6H4-C1),7.53 (d, 8H, J = 19.0 Hz, =CH-Ar)13C NMR (C6D6, ppm): delta = 117.9 (=CHSi), 128.5 (o-C of CeiijCl), 129.2 (m-C of C6H4C1), 135.5 (ipso-C at CI of Q^Cl), 135.7 (ipso-C of C6H4C1), 149.1(=CHAr)29Si NMR (C6D6, ppm): delta = -78.06APPI-MS: m/z ([M+H]+, percent 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) |