Unusual synthesis,structure, and thermochromic properties of novel sterically hindered cyclohexadienes

Oxidation of 4--morpholino--(2-hydroxyphenyl)]methyl-2,6-di-(tert-butyl)-phenol (I) follows an unusual course, with formal loss of the benzyl carbon atom, to give 2,6-di(tert-butyl)-4-morpholino-4-(2-hydroxyphenyl)cyclohexa-2,5-dienone (II), which is thermochromic in solution. This property is due to the dissociation of (II) into morpholine and 3,5-di(tert-butyl)-2,4-diphenoxyquinone. The structure of (II) was established directly by x-ray diffraction, which enabled its conformational features to be related to its thermochromic properties. An x-ray examination of 3,3,5,5-tetra(tertbutyl)-2,4-diphenoquinone (X), together with the direct synthesis of the thermochromic analog of (II) (2,6-di(tert-butyl)-4-morpholino-4-2-hydroxy-3,5-di(tert-butyl)phenyl]cyclohexa-2,5-dienone) (XI) from (X) and morpholine, confirmed the proposed mechanism of thermochromic dissociation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1121–1129, May, 1991.The authors thank V. I. Minkin and A. S. Morkovnik for participating in discussions of this work.