ChemInform Abstract: Catalytic Bromination of Adamantane in 1,1,2‐Trichloro‐1,1,2‐trifluoroethane and Perfluorobenzene.

Reactions of adamantanes in electrophilic media

“…68 The reaction of adamantane (1) with bromine in the presence of Fe in Freon-113 (1,1,2-trichloro-1,2,2-trifluoroethane) or in hexafluorobenzene affords dibromide 19 in 97.3% yield and of 99% purity. 69 A complex mixture of products comprising 1,3,5trichloro-(37, 27.3%), 1-bromo-3,5-dichloro-(16.6%), 1,3dibromo-5-chloro-(27.4%), 1,3,5-tribromo-(12.0%), 1-bromo-3,5,7-trichloro-(10.8%) and 1,3-dibromo-5,7-dichloro-adamantanes (5%) were obtained in the presence of AlCl 3 . 69 The treatment of adamantane (1) with bromine at 100 8C under 27.2 atm also yields 1,3-dibromoadamantane.…”

“…69 A complex mixture of products comprising 1,3,5trichloro-(37, 27.3%), 1-bromo-3,5-dichloro-(16.6%), 1,3dibromo-5-chloro-(27.4%), 1,3,5-tribromo-(12.0%), 1-bromo-3,5,7-trichloro-(10.8%) and 1,3-dibromo-5,7-dichloro-adamantanes (5%) were obtained in the presence of AlCl 3 . 69 The treatment of adamantane (1) with bromine at 100 8C under 27.2 atm also yields 1,3-dibromoadamantane. 70 1,3,5,7-Tetrabromoadamantane (43) has been obtained in 75% yield by heating 1,3,5-tribromoadamantane (44) with bromine and AlBr 3 in an autoclave at 150 8C for 2 h. 16 Synthesis of 1,3,5,7-tetrabromoadamantane (43) by bromination of adamantane (1) has also been performed under relatively mild reaction conditions (an equimolar amount of AlCl 3 , 30 min at 20 8C and then 3 h at 60 8C).…”

“…1-Phenyladamantane (67) reacts with bromine under reflux to give a mixture of products from which no individual compound was isolated; 118 however, 1-(4-bromophenyl)adamantane ( 68) was obtained at 0 8C, and 1-(3,4-dibromophenyl)adamantane (69) as the product of substitution of two hydrogen atoms in the aromatic ring was prepared at 25 8C. 119 The introduction of the carboxy group into position 3 of the adamantane nucleus in 1-phenyladamantane does not affect the character of the phenyl ring substitution.…”