88799-00-2Relevant academic research and scientific papers
REDUCTION OF KETOXIMES WITH THE BICYCLOHEPTANE AND TRICYCLO2,6>HEPTANE STRUCTURES
Ordubadi, M. D.,Pekhk, T. I.,Belikova, N. A.,Rakhmanchik, T. M.,Plate, A. F.
, p. 678 - 683 (2007/10/02)
Only the corresponding primary amines were obtained during the reduction of the oximes of bicycloheptan-2-one and 1-methyl- and 1-ethylbicycloheptan-2-ones with sodium in alcohol, whereas mixtures of primary amines and 3-azabicyclooctanes were formed with lithium aluminium hydride.The yield of the last products increases with inctrease in the reaction temperature.Only primary amines were obtaines during the reduction of the 1-methyl- and 1-ethyltricyclo2,6>heptan-3-ones oximes both with sodium in alcohol and with lithium aluminum hydride.
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.
