Premium
Preparation and Synthetic Utility of 1‐Trimethylsiloxyalkyl‐bis(trimethylsilyl)silanes, (Me 3 Si) 2 SiH–C(OSiMe 3 )R 1 R 2
Author(s) -
Luderer Frank,
Reinke Helmut,
Oehme Hartmut
Publication year - 1998
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/(sici)1521-3749(199809)624:9<1519::aid-zaac1519>3.0.co;2-c
Subject(s) - silanes , trimethylsilyl , chemistry , silane , isomerization , hydrolysis , medicinal chemistry , silylation , tris , polymer chemistry , organic chemistry , catalysis , biochemistry
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.