770-92-3Relevant articles and documents
Pyrolysis of Three Acetates of Methylbicycloheptan-2-ols and the Parent Alcohols
Vainiotalo, Pirjo,Pohjala, Esko,Maelkoenen, Pentti
, p. 1537 - 1540 (2007/10/02)
The acetates of exo-2-methyl-endo-bicycloheptan-2-ol, endo-2-methyl-exo-bicycloheptan-2-ol, and 1-methyl-exo-bicycloheptan-2-ol together the parent alcohols have been pyrolysed at several temperatures and the product distribution determined.The mechanism and direction of elimination in relation to structure are discussed qualitatively.The formation of the principal products is consistent with a concerted elimination involving a six-membered cyclic transition state.Wagner-Meerwein rearrangement occurs as a competing reaction in cases where the formation of a tertiary structure is possible at the expense of a secondary one.In the case studied a two-step reaction is considerably faster than direct pyrolysis of the secondary structure.
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).
