16651-54-0Relevant academic research and scientific papers
Deamination Reactions, 39. Decomposition of 1-Methylnorbornane-2-diazonium Ions
Banert, Klaus,Kirmse, Wolfgang,Wroblowsky, Heinz-Juergen
, p. 3591 - 3610 (2007/10/02)
Nitrous acid deaminations of 1-methyl-exo-2-norbornylamine (19) and of the epimeric 2-methyl-2-norbornylamines (32, 34) in water yielded endo-2-methyl-exo-2-norbornanol (42a) exclusively.In contrast, 1-methyl-endo-2-norbornylamine (23) afforded 2-methylbicycloheptan-2-ol (13a, 20percent) and 1-methyl-endo-2-norbornanol (14a, 17percent) in addition to 42a.The formation of bicycloheptyl derivatives 13 is accentuated by better nucleophiles, as shown by photolyses of 1-methyl-2-norbornanone tosylhydrazone (35) in methanol/methoxide, and in the presence of lithium azide. 14 and (in part) 13 are thought to originate from 7-bridged 1-methylnorbornyl cations (10).A substantial fraction of 13 stems from the open 2-methylbicycloheptyl cation (12).The contributions of 10 and 12 have been elucidated by means of 3-D2 labels.Introduction of an exo-3-methyl group (48, 50) enhances participation of the C-1 - C-7 bond.Cations 57 and 61 are the predominant intermediates generated from 1,exo-3-dimethylnorbornane-endo-2-diazonium ions (53).Less polar solvents (acetic acid, 2-ethylhexanoic acid) induce variations in product distribution which are attributed to increasing solvolytic displacement (ks) and ion pair collapse.
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).
