The Acid-Induced Rearrangement of 1-Hydroxyalkyltris(trimethylsilyl)silanes

✍ Scribed by Katrin Sternberg; Hartmut Oehme

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 421 KB
• Volume: 1998
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/(sici)1099-0682(199802)1998:2<177::aid-ejic177>3.0.co;2-d

✦ Synopsis

In the presence of strong acids, such as HCl or H 2 SO 4 , 1-Si(OSO 3 H)ϪC(SiMe 3 )HMes (5) was isolated. 5 is the intermediate in the H 2 SO 4 -catalyzed isomerization of 1d and was hydroxyalkyltris(trimethylsilyl)silanes (Me 3 Si) 3 SiϪC(OH)R 1 -R 2 (1a؊f) isomerize by 1,2-Me 3 Si/OH exchange to give the converted in situ with methanol, acetic anhydride, HF or HCl to give the respective methoxysilane 6, acetoxysilane 7, fluo-

R 2 : a: Me, Me; b: H, 4-MeC 6 H 4 ; c: H, 4-iPrC 6 H 4 ; rosilane 8, or chlorosilane 9. Deprotonation of 4a, d, f with sodium hydride causes a further rearrangement, a 1,3-C,O-d: H, Mes; e: H, 2-Me 2 NC 6 H 4 ; f: H, 2,4,6-(MeO) 3 C 6 H 2 ]. A mechanism for the isomerization is proposed. In the case of trimethylsilyl migration, to give the siloxanes (Me 3 Si) 2 (Me 3- SiO)SiϪCHR 1 R 2 (11a, d, f). the reaction of 1d with sulfuric acid, the silylsulfate (Me 3 Si) 2 -