Reactivity in solid phase. Transformations of 2,4-di-tert-butylphenol and its derivatives under elastic deformation conditions

The solid-phase transformations of 2,4-di-tert-butylphenol (1) and its 6-bromo- (5) or 6-hydroxymetyl-substituted (11) derivatives were studied. The dependence of the behavior of compounds1 and5 in solid-phase processes on the composition of the medium was found. Oxidative coupling with the participation of atmospheric oxygen as an oxidant became possible at an excess of NaOH (or in NaOH/NaCl medium). The mechanism of oxidative debromocondensation of compound 5 that involves spontaneous dehalogenation of the haloquinolide intermediate and heterolysis of the C-Br bond with the elimination of Br⁺ was proposed. It was concluded that the mechanism proposed is common to solid-phase dienone-phenol transformations. The dual reactivity of compound11, determined by the chemical hardness of the anion-catalyst, was discovered.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1499–1503, June, 1996.