Stabilization of long-chain intermediates in solution. Octyl radicals and cations

The rearrangements of 1-octyl, 1-decyl and 1-tridecyl intermediates obtained from thermal lead(IV) acetate (LTA) decarboxylation of nonanoic, undecanoic and tetradecanoic acid were investigated experimentally through analysis and distribution of the products. The relationships between 1,5-, 1,6- and possibly existing 1,7-homolytic hydrogen transfer in 1-octyl-radical, as well as successive 1,2-hydride shift in corresponding cation have been computed via Monte-Carlo method. Taking into account that ratios of 1,5-/1,6-homolytic rearrangements in 1-octyl- and 1-tridecyl radical are approximately the same, the simulation shows very low involvement of 1,7-hydrogen rearrangement (1,5-/1,6-/1,7-hydrogen rearrangement = 85:31:1) in 1-octyl radical.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Rearrangements products distribution study of the long-chain radicals and cations. ► Monte Carlo simulation of the stabilization processes of 1-octyl radical. ► Ratio of homolitical rearrangements determined by Monte Carlo simulation.