有機ケイ素化合物の合成(第14報) : o-(Trimethylsilyl)phenolに対する親電子試薬の反応について

概要

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Reaction of o-(trimethylsilyl)phenol (I) with various electrophilic reagents was examined. Acid and alkali treatment of I results in the severance of silicon-aryl bond and phenol is formed. Bromination of I results in substitution of the position para to the hydroxyl, accompanied by desilylation and p-bromophenol is formed. Coupling reaction of I with benzenediazonium chloride results in the substitution first in the position para to the hydroxyl and then at ortho to form 2-trimethylsilyl-4-(phenylazo)phenol (IV) and then 2-trimethylsilyl-4,6-bis(phenylazo)phenol (IX), and no further substitution occurs. This is considered to the due to the stabilization of the silicon-aryl bond by the -I effect of the second substitution. Nitration of I with acetyl nitrate at 20° or -50° failed to produce any nitrated product. The Reimer-Tiemann reaction of I gave salicylaldehyde, while the Friedel-Crafts reaction of the methyl ether (XV) of I with aluminum chloride and acetyl or benzoyl chloride afforded p-methoxyacetophenone or p-methoxybenzophenone.
公益社団法人日本薬学会の論文
1967-05-25