Date: August 1987
Creator: Bobbitt, Kevin L. (Kevin Lee)
Description: We report the attempted syntheses of two photochemical dimethylsilene precursors, both of which are derived from polyphenyl silanorbornadiene skeletons. Possible synthetic schemes and our results are reported herein. Photolysis of 1,2-divinyl-1,1,2,2-tetramethyl-1,2-disilane at room temperature in a cyclohexane solution of 1,3-butadiene produces 1,1-dimethyl-2-(vinyldimethylsilylmethyl) silene which is trapped in high yields to afford the E- and Z-1,1-dimethyl-2-(vinyldimethylsilylmethyl)-3-vinyl-1-silacyclobutanes in 42 and 29% yields, respectively, along with minor amounts of 1,1-dimethyl-2-(vinyldimethylsilylmethyl)-1-silacyclohex-3-ene, 9%. Low Pressure Flow Pyrolysis at 450º C of either the E- or Z-isomer provides a relatively mild thermal source of the silene in the gas phase. Two products, 1,1,3,3-tetramethyldisilacyclohex-3-ene and 2,2,5,5-tetramethyl-2,5-disilabicyclo[2.2.1]hexane, are formed from an intramolecular rearrangement of the silene. Other reactions of the 3-vinylsilacyclobutanes include geometric isomerization, ring expansion to the silacyclohex-3-ene, and a homodienyl-1,5-hydrogen shift to 3,3,6,6-tetramethyl-3,6-disiladeca-1,4,8-triene. Synthetic schemes, successful and unsuccessful, for hydrido silene, acylpolysilene, and fluorine substituted silene precursors are discussed in the final chapter.
Contributing Partner: UNT Libraries