68069-59-0Relevant academic research and scientific papers
222. Inductivity and Bridging in 2-Bicyclooctyl Cations. Polar Effects, Part II.
Grob, Cyril A.,Sawlewicz, Pawel
, p. 1906 - 1917 (1984)
The solvolysis rates and products of several 6-substituted 2-exo- and 2-endo-bicyclooctyl p-toluenesulfonates, 12 and 13, respectively, are reported.Inductivity, as measured by the reaction constants pI, is considerably less in the exo-series 12 (pI = -1.50) than in the corresponding 2-exo-norbornyl p-toluenesulfonates 1 (pI = -2.0).It is proposed that, for geometrical reasons, bridging of the cationic center C(2) by C(6) is not as strong in the bicyclooctane series 12 as it is in the norbornane series 1.On the other hand, inductivity is higher in the 2-endo-bicyclooctane series 13 (pI = -1.0) than in the corresponding 2-endo-norbornane series 3 (pI = 0.78), probably, because in the former case bridging of C(6) is less hindered by the departing anion.The relative yields of exo- and endo-substitution products from the series 12 and 13, are in accord with graded bridging of C(6) in the incipient bicyclooctyl cations.But almost constant bridging of C(2) by C(7) is indicated in the ionization of the 2-endo-bicyclooctane series 13.Consequently, in the free unsubstituted bicyclooctane cation C(2) is bridged symmetrically by C(6) and C(7), in contrast to the current concept of 'non-classical' two-electron-three-center bonding.
216. Bicyclooctanes. Syntheses and Hydrolyses of 6-exo-substituted 2-exo- and 2-endo-Bicyclooctyl p-Toluenesulfonates. Part 9
Grob, Cyril A.,Sawlewicz, Pawel
, p. 1859 - 1867 (2007/10/02)
The synthesis of the title compounds and their hydrolysis products in 70percent dioxane are described.
