Syntheses of F-Adamantyl Polychlorides and F-1-Norbornyl Chloride: The First Documented 1,3-Chlorine Shift

1,2-Dichloro-F-adamantane, 1,3-dichloro-F-adamantane, 1,3,5-trichloro-F-adamantane, 1,3,5,7-tetrachloro-F-adamantane, and 1-chloro-F-norbornane have been synthesized by aerosol direct fluorination from their corresponding hydrocarbons for the first time. All compounds have been characterized by ¹⁹F NMR, FT-IR, mass spectrometry, and elemental analysis. The aerosol direct fluorination of 2,2-dichloroadamantane produced a mixture of two dichloro-F-adamantanes plus a trace amount of 2-chloro-F-adamantane (chlorine loss product). The mixture of dichlorinated products indicated that chlorine shifts during this aerosol direct fluorination had occurred. The high probability of a 1,3-chlorine shift versus sequential 1,2-chlorine shifts or intermolecular chlorine redistribution is discussed.