22768-96-3Relevant articles and documents
Norpinyl-Norbornyl Rearrangements: 2-Methyl- and 2,exo-6-Dimethylbicycloheptane Derivatives
Banert, Klaus,Kirmse, Wolfgang,Wroblowsky, Heinz-Juergen
, p. 2474 - 2485 (2007/10/02)
Solvolyses of 2-methylbicyclohept-2-yl-4-nitrobenzoate (9), the nitrous acid deamination of the corresponding amine (4e), and acid-catalyzed rearrangements of various 2-methylbicycloheptane derivatives (4a - c) have been investigated. 2-Methylbicycloheptyl (4) and 1-methyl-endo-2-norbornyl (10) products prevailed; minor quantities of 2-methyl-exo-2-norbornyl derivatives (12) were also obtained.The product distributions were independent of the precursor but were strongly affected by the nucleophilicity of the solvent.Our observations are consistent with the 7-bridged norbornyl cation 6 as the predominant intermediate.Further stabilization of 6 by exo-3-methyl substitution is indicated by the results of the acid-catalyzed rearrangement of 2,exo-6-dimethylbicycloheptan-2-ol (17).