Collect. Czech. Chem. Commun. 1984, 49, 1774-1779

Beckmann rearrangement of adamantanone oxime as a route to ditopic and tritopic secondarily substituted adamantane derivatives

Jan Třískaa, Luděk Vodičkaa, Eugenijus P. Butkusb and Milan Hájeka

a Laboratory of Synthetic Fuels, Prague Institute of Chemical Technology, 166 28 Prague 6
b Department of Chemistry, Vilnius V. Kapsukas State University, 322006 Vilnius, USSR


The reaction in mixtures of adamantanone with hydroxylamine hydrochloride was studied in hydrochloric, hydrobromic, and hydroiodic acid solutions. In hydrochloric and hydroiodic acids, mixtures of isomers of 4-chloroadamantan-2-one and 4-iodoadamantan-2-one, respectively, are formed, whereas in hydrobromic acid in the presence of excess hydroxylamine hydrochloride, three stereoisomers of 4,8-dibromoadamantan-2-one appear. All the stereoisomeric haloketones were isolated by elution adsorption chromatography on silica gel or by crystalization. For the pure substances, their infrared, mass, and NMR spectra were measured.