52428-01-0Relevant articles and documents
Homolytic Ring Fission reactions of Bicycloalkanes and Bicycloalk-2-yl Radicals: Electron Spin Resonance Study of Cycloalkenylmethyl Radicals
Roberts, Charles,Walton, John C.
, p. 879 - 886 (2007/10/02)
Hydrogen abstraction from bicycloalkanes (n=3-6) by t-butoxyl radicals was examined by an e.s.r. technique.The main site of attack was C(2) giving bicycloalk-2-yl radicals which rearranged by β-scission of the outer cyclopropane bonds to give cycloalkenylmethyl radicals.This is in contrast to the bicycloalk-2-yl radicals (n=1,2) which rearranged by fission of the inter-ring bonds to give cycloalkenyl radicals. β-Scission in bicycloalk-2-yl radicals was examined by semi-empirical SCF MO calculations.The conformations and barriers to internal rotation of the cycloalkenylmethyl radicals were determined from the variation in the β-H hyperfine splitting constants with temperature.Photobromination of bicycloalkanes (n=3,4) was also investigated in CCl4 solution.The main process was bimolecular homolytic substitution (SH2) by bromine atoms at the cyclopropane carbons, but there was an increase in hydrogen abstraction with ring size.The SH2 reactions parallel the β-scission reactions of the bicycloalk-2-yl radicals in that the main bond undergoing fission changes from the inter-ring bond to the outer cyclopropane bond as the ring size increases.
