Karen J. Skinner, R. Blaskiewicz, J. McBride
1972
Citations
0
Influential Citations
11
Citations
Journal
Israel Journal of Chemistry
Abstract
The 3-phenyl-3-pentyl radicals from photolysis of azobis-3-phenyl-3-pentane (APP) in solution give 3,4-diethyl-3,4-diphenylhexane and a photolabile product assumed to arise by para coupling. Photolysis of APP as a crystalline solid at −78° gives the disproportionation products 3-phenylpentane (PPH) and 3-phenyl-2-pentene (PP) as a 3:1 mixture of the E and Z isomers. This stereoisomeric ratio is surprising in terms of the solid-state molecular conformations, for which a topochemical scheme predicts predominance of the Z isomer. Isotopic distributions in PPH, Z-PP and E-PP from photolysis of solid APP which was 82% deuterated in its methylene groups shows: (1) that Z-PP is formed under strong lattice control; (2) that E-PP is formed in a process with greater, but not complete, molecular freedom; and (3) that there is often a dynamic competition for hydrogen-atom donation between the two radicals involved in disproportionation.