Reactivities of Stable Rotamers. XLII. Generation and Fates of Rotameric [1-(9-Fluorenyl)-2-naphthyl]methyl Radicals

Abstract

Abstract The title radical rotamers were generated by thermolyses of the corresponding t-butyl peroxycarboxylates or photolyses of the corresponding 2(1H)-thioxo-1-pyridyl carboxylates. Products from the t-butyl peroxyesters were t-butoxy compounds, dimers, and colligation products with a benzyl radical, when the reactions were carried out in toluene. In carbon tetrachloride, chlorine-abstraction products and colligation products with a trichloromethyl radical were obtained in addition to the dimers. Photolyses of the 2(1H)-thioxo-1-pyridyl esters afforded expected products, the dimers and 2-pyridylthio derivatives. Generally, the differences from one rotamer to another cause minor differences in the distribution of the products. The small differences are attributed to the steric effects which operate at the site where the radical is produced.