40488-88-8Relevant articles and documents
Rearrangements of Pentacyclododecyl Cations
Kirmse, Wolfgang,Ritzer, Joachim
, p. 4965 - 4986 (2007/10/02)
Pentacyclododecyl cations (29-32) have been investigated as models for distorted 2-norbornyl cations.When 30 and 32 were generated by solvolysis (brosylates 8 and 20) or by nitrous acid deamination (amines 10 and 21), Wagner-Meerwein rearrangement occured competitively with solvent capture.Both epimeric precursors, 3x and 3n, reacted with high exo-selectivity.In contrast, endo-precursors 2n (12, 13) produced major quantities of endo-products.Retentive displacement at 2n is attributed to intervention of the bridged ion 29, generated independently by protonation of the hexacyclododecane 28.A rapid, degenerate alkyl shift in 30 was detected by means of a deuterium label (-30 -30).Subsequent rearrangement(-30 --> -32) suggests that the bridged structure 31 is not significantly lower in energy than 30.- Thus, pentacyclododecyl cations show several features uncommon to a norbornyl system: (1) relatively slow Wagner-Meerwein rearrangement, (2) fast endo,endo-3,2-shifts, and (3) abundant formation of 29 (a 7-bridged norbornyl cation), all explicable in terms of the distorted norbornyl geometry. - Less nucleophilic media led to fragmentation of 30 and/or 32.In trifluoroacetic acid the tetracyclododecenyl cation 64 was formed and trapped selectively.The dehydration of 7 on alumina (275 deg C) provided a convenient route to the alkene 17.Minor products (47, 50, 51) arose via competitive fragmentation-elimination paths.
Steric Effects on Reaction Rates - III. Application of Force-Field Calculations to Chromic Acid Oxidation of Alcohols
Mueller, Paul,Blanc, Jacky,Lenoir, Dieter
, p. 1212 - 1220 (2007/10/02)
The rates of oxidation with chromic acid of 15 bi- and polycyclic secondary alcohols have been measured and correlated with strain changes calculated by the MM1-program between the alcohols and the corresponding ketones.A correlation of the same quality is obtained upon representation of OH-strain by CH3-strain.The significance of the correlations with respect to the oxidation mechanism as well as the limitations of the applicability of force-field calculations to reactivity problems are discussed.