Anodic oxidation of α,α′-bis(trimethylsilyl)xylenes in alcohols

✍ Scribed by Toshio Koizumi; Toshio Fuchigami; Tsutomu Nonaka

• Book ID: 103062717
• Publisher: Elsevier Science
• Year: 1988
• Tongue: English
• Weight: 583 KB
• Volume: 33
• Category: Article
• ISSN: 0013-4686
• DOI: 10.1016/0013-4686(88)80236-6

✦ Synopsis

Anodic oxidation of a,cz'-bis(trimethylsilyl)-o-, -m-, and -p-xylenes (l-3) was comparativety examined. a-Trimethyliilylation of xylenes markedly decreased their oxidation potentials while additional a'trimethylsilylation resulted in no further change. The silylxylenes I-3 underwent anodic alkoxylation in various alcohols accompanying elimination of a trimethylsilyl group to provide the corresponding monoalkoxylated products solely. The efficiency of alkoxylation greatly depended not only on the molecular structures of the substrates but also on those of alcohols and counter anions of supporting electrolytes.

From the results, it was suggested that the anodic substitution with alcohols was greatly affected not only by the nature of stabilization of cationic intermediates but also by steric hinderance and electrostatic interaction between the trimethylsilyl group and alcohols as nucleophiles.