Lithium Perchlorate as a Reagent for Synthesis of Covalently Bonded Organic Perchlorates via Electrophilic Additions of Halogens and Nitronium Tetrafluoroborate to Olefins

The reaction of a series of olefins with chlorine and bromine in the presence of a large excess of lithium Perchlorate in ether gave 1,2-halo Perchlorates together with the corresponding 1,2-dihalides. Analogous reactions of NO₂BF₄ in the presence of LiClO₄ in methylene chloride or ethyl acetate with monoolefins gave 1,2-nitro Perchlorates. Norbornadiene reacted with a NO₂BF₄/LiClO₄ system to give two isomeric nitro Perchlorates of nortricyclenic structure. Several synthetic and mechanistic aspects of this new reaction of electrophilic perchloration of olefins are discussed.