ChemInform Abstract: A CONVENIENT PREPARATION OF SUBSTITUTED PHENYL ADAMANTANES FROM 1‐BROMOADAMANTANE

Electrophilic aromatic substitution. Part 30. The effects of the p-bicyclo[2.2.2]octan-1-yl, adamantan-1-yl, exo- and endo-norbornan-2-yl, and neopentyl substituents in detritiation. Steric acceleration of hyperconjugation

“…PhenyZadamantane.-The general routes used above cannot be employed to prepare 1-(4-bromopheny1)adamantane because the adamantyl group apparently substitutes into more than one benzene ring; 2o one would also expect that more than one adamantyl group would substitute into each benzene ring, this being the usual observation for alkylation ; these problems of polysubstitution can now be avoided by the use of iron(Ir1) chloride as catalyst. 21 Topsom and his co-workers used the alternative low-temperature (this we find is critical) adamantylation of bromobenzene using aluminium chloride as catalyst. By this route we obtained 1-(4-bromopheny1)adamantane (61y0), m.p.…”

Reactions of adamantanes in electrophilic media

“…The synthesis of some other adamantane-substituted aromatic compounds was also described. 207,208 Either adamantane with several phenyl groups or benzene bearing up to three adamantyl substituents are formed in the reaction of 1-bromoadamantane (2) with benzene in the presence of Lewis acids, depending on the ratio of the reactants. 209,210 1,3,5-Triadamantylbenzene (110) has been synthesised by the reaction of benzene or 1-phenyladamantane (67) with 1-bromoadamantane (2) in liquid SO 2 in the presence of AlCl 3 .…”

Indium-Catalyzed Friedel-Crafts Alkylation of Monosubstituted Benzenes by 1-Bromoadamantane

“…100°C was reported for the successful monoadamantylation of monosubstituted benzenes with formation of only the para isomer. 15,16 Subsequently, a more systematic study of the reaction was described by Olah et al using boron tris(triflate) as a very efficient, although unselective, catalyst. 17 Olah, Török et al subsequently showed that substituted benzenes could be adamantylated with high regioselectivity for the para isomer by using various supported acid catalysts at 111°C.…”