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

✍ Scribed by Kazem D. Safa; Shahin Tofangdarzadeh; Hossein Heydari Ayenadeh

• Publisher: John Wiley and Sons
• Year: 2008
• Tongue: English
• Weight: 386 KB
• Volume: 19
• Category: Article
• ISSN: 1042-7163
• DOI: 10.1002/hc.20440

✦ Synopsis

Abstract

Tris(dimethylsilyl)methane, (HMe~2~Si)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 (H~2~PtCl~6~ċ6H~2~O) in air to give products (ROMe~2~Si)~3~CH (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, (PhCH~2~)~2~O and HC(Me~2~SiOSiMe~2~)~3~CH, respectively. The compound (n‐BuOMe~2~Si)~3~CSiMe~2~H was made from (n‐BuOMe~2~Si)~3~CH by treatment with lithium diisopropylamide, followed by quenching with HMe~2~SiCl. 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 (HMe~2~Si)~3~C groups were linked to them by nucleophilic substitution reactions between (HMe~2~Si)~3~CLi 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