40317-63-3Relevant academic research and scientific papers
Hydrogenolysis of Small Cycloalkanes, XIII - Hydrogenation of Homucubane Derivatives
Osawa, Eiji,Schneider, Ingrid,Toyne, Kennet J.,Musso, Hans
, p. 2350 - 2361 (2007/10/02)
Two dihydro products 5a and 7a are formed by hydrogenation of homocubane (6a) with Pd-, Pt-, and Rh-catalysts.Only the unsymmetric 7a reacts further to give twistbrendane (8a).In addition, ca. 20percent brendane (11a) is obtained by hydrogenation of homocuneane (9a), which is formed from 6a by rearrangement on the catalyst.The yield of the symmetric dihydro product 5b is raised up to 40percent in the case of hydrogenation of the ethylene acetal 6b of the 9-ketone on Rh/Al2O3.With the ester 6d no 5d is obtained but 7d and 8d only.
Evidence for 4-Homocubyl Carbenium Ions as Reactive Intermediates
Mergelsberg, Ingrid,Langhals, Heinz,Ruechardt, Christoph
, p. 360 - 366 (2007/10/02)
4-(Hexafluoroisopropoxy)homocubane (6) is the main product of the thermolysis reaction of N-(4-homocubyl)-N-nitrosoacetamide (9) and of the solvolysis reaction of 4-homocubyl bromide (5) in hexafluoro-2-propanol.This is experimental evidence for 4-homocubyl carbenium ions as intermediates in both reactions.The solvolysis rate of 4-homocubyl bromide at 120 deg C in the same solvent (k1120deg C = 1.3 * 10-7 s-1) by far exceeds that of 1-norbornyl bromide which does not react at a detectable rate under these conditions.According to force field calculations the strain enthalpy is increasing by as much as 66 kcal * mol-1 in the ionisation of 4-homocubyl bromide.Therefore nonclassical stabilization of the 4-homocubyl carbenium ion is postulated.
