Reactions of tris(dimethylsilyl)methane and polymers containing si—h groups with various hydroxy compounds under aerobic and mild conditions

Abstract

AbstractTris(dimethylsilyl)methane, (HMe2Si)CH, reacts with n‐propyl, iso‐propyl, n‐butyl, s‐butyl, iso‐butyl, n‐pentyl, s‐pentyl, n‐hexyl alcohol, and phenol in the presence of chloroplatinic acid (H2PtCl6ċ6H2O) in air to give products (ROMe2Si)3CH (where R is n‐propyl, iso‐propyl, n‐butyl, s‐butyl, iso‐butyl, n‐pentyl, s‐pentyl, n‐hexyl, phenyl). Similar reactions with benzyl alcohol and acetic acid lead to the unexpected products, (PhCH2)2O and HC(Me2SiOSiMe2)3CH, respectively. The compound (n‐BuOMe2Si)3CSiMe2H was made from (n‐BuOMe2Si)3CH by treatment with lithium diisopropylamide, followed by quenching with HMe2SiCl. The homopolymer poly{(4‐chloromethyl)styrene} and copolymers with styrene (in 1:1 and 1:3 mol ratio) were synthesized by free radical polymerization, and (HMe2Si)3C groups were linked to them by nucleophilic substitution reactions between (HMe2Si)3CLi and the chloromethyl groups of the polymer side chains. The resulting functional polymers containing Si—H bonds reacted with various alcohols in the presence of chloroplatinic acid under heterogeneous conditions. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:365–376, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20440