有機珪素化合物の合成 (第7報)

3-Trimethylsilylphenolに対するカチオノイド試薬の反応について

抄録

Various kinds of cationoid reagent were reacted with 3-trimethylsilylphenol (II). Reaction with bromine resulted in primary and secondary substitutions in 4- and 6-positions to afford 3-trimethylsilyl-4-bromophenol and 2, 4-dibromo-5-trimethylsilylphenol. The third substitution occured at either 2- or 3-position and further bromination gave 2, 3, 4, 6-tetrabromophenol. Diazo coupling took place in 4-position and reduction of the azo compound so obtained afforded 3-trimethylsilyl-4-aminophenol. Nitration of the acetate of (II) with acetyl nitrate was difficult. Friedel-Crafts reaction of (II) by application of anhydrous aluminium chloride and acetic anhydride to its methyl ether afforded p-methoxyacetophenone. Fries reaction of (II) by application of anhydrous aluminium chloride to its acetate gave o- and p-hydroxyacetophenone, while Reimer-Tiemann reaction by application of chloroform and potassium hydroxide gave 4-trimethylsilylsalicylaldehyde. Nitrosation with nitrous acid gave 3-trimethylsilyl-4-nitrosophenol and its catalytic reduction afforded the corresponding amine.