Preparation and Synthetic Utility of 1-Trimethylsiloxyalkyl-bis(trimethylsilyl)silanes, (Me3Si)2SiH–C(OSiMe3)R1R2

✍ Scribed by Frank Luderer; Helmut Reinke; Hartmut Oehme

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: German
• Weight: 157 KB
• Volume: 624
• Category: Article
• ISSN: 0372-7874
• DOI: 10.1002/(sici)1521-3749(199809)624:9<1519::aid-zaac1519>3.0.co;2-c

✦ Synopsis

1-Trimethylsiloxyalkyl-bis(trimethylsilyl)silanes ( 5), obtained by a base induced isomerization of easily accessable 1-hydroxyalkyl-tris(trimethylsilyl)silanes (1) were hydrolized to give 1-hydroxyalkyl-bis(trimethylsilyl)silanes ( 6), which in presence of sodium hydride underwent a further 1,3-Si,O-trimethylsilyl migration resulting in the formation of 1-trimethylsiloxyalkyl-disilanes Me 3 SiSiH 2 ±C(OSiMe 3 )R 1 R 2 (7). Under acidic conditions, the alkoxysilanes 5 isomerized in a Me 3 Si/OSiMe 3 exchange under formation of the 1-trimethylsilylalkyldisiloxanes 10, which were hydrolyzed affording the silanols 11. Chlorination of the H-silanes 5 with CCl 4 gave the chlorosilanes 12, which underwent rapid thermal isomerizations to give via the 1-chloroalkyldisiloxanes 13 the 1-trimethylsilylalkyl-chlorodisiloxanes 15. Hydrolysis of 12 or 15, resp., finally afforded the 1-trimethylsilylalkyl-silanediols 18. Possible mechanisms of the various isomerization processes are discussed. The structures of the products described were elucidated by full spectral analyses. For 18 a the results of an X-ray structural analysis are given.