G. Olah, P. Ramaiah, C. B. Rao
Aug 1, 1993
Citations
0
Influential Citations
48
Citations
Journal
Journal of the American Chemical Society
Abstract
The slow reaction of adamantane with nitronium tetrafluoroborate at room temperature in purified, nitrile-free nitromethane or in nitroethane gives 1-nitroadamantane in 66% and 74% isolated yield, respectively. Similar reaction of diamantane gives 62% 1- and 5% 4-nitrodiamantane. Initial reaction upon aqueous workup gives 1-adamantanol with 1-fluoroadamantane, 3-fluoro-1-adamantanol, and adamantanone as byproducts. Upon prolonged reaction 1-nitroadamantane is formed in good yield. The experimental data are in accord with intermediate formation of the 1-adamantyl cation (by hydride abstraction or cleavage of initially formed 1-nitroadamantane) followed by reaction with HNO 2 or NO 2 - formed in the reaction, giving 1-adamantyl nitrite, which then undergoes cleavage-rearrangement to give 1-nitroadamantane