The Reaction of Phenols with Tertiary Butyl Chloride

Abstract

The first reaction is characterized by recovery of the unchanged phenolic compound and evolution of a gaseous olefine, the second by the formation of a phenolic compound, and the third by the formation of a high boiling, alkali insoluble ether. All three types of reaction have been reported in the literature, but no attempt has been made to ascertain whether or not the relative importance of these reactions is affected by the nature of the phenolic compound used. Perhaps the most outstanding feature of the literature on this subject, aside from its scarcity, is its lack of variety in the compounds used. Only two articles were discovered which mentioned the reaction between tertiary butyl chloride and any phenolic compound other than phenol itself. In 1899 A. Gurewitsch (1) reported the formation of the readily decomposed mono-tertiary butyl ether of di-tertiary-butylresorcinol from the reaction of tertiarybutyl chloride with resorcinol in the presence of ferric chloride. Two years later, Speigel and Sabbath (2) described their failure to obtain any reaction other than the formation of isobutylene from the reaction between tertiarybutyl chloride and p-nitrophenol. Even the postassium salt of p-nitrophenol and tertiary-butyl chloride at 140? C and 20-24 atmospheres pressure gave only isobutylene and p-nitrophenol (Reaction I). The silver salt at room temperature and at atmospheric pressure reacted with the tertiary-butyl chloride in the same manner. Lewis (3) reported the formation of p-tertiary-butylphenol in fair yields along with a negligible quantity of a high boiling alkali-insoluble material when tertiary-butyl chloride was allowed to react with sodium phenate.