Decomposition of endo- and exo-(2-Norbornyl)formyl m-Chlorobenzoyl Peroxides

Article abstract of DOI:10.1021/jo00339a002

The subject peroxides undergo first-order decomposition in several solvents with rates increasing moderately with solvent polarity and endo/exo rates in a ratio of 1:10-100.Carboxyl inversion product, ROCOOCOAr, and other "polar" products are formed with no evidence for significant free-radical production.Products from an exo-peroxide have exclusively exo configurations, but carboxyl inversion product from endo peroxide contains small amounts of exo isomer.In acetic acid, 2-norbornyl acetate is a major product, with endo/exo ratio of 14:86 from the endo-peroxide.Optically active exo-peroxide in acetic acid gives exo-2-norbornyl acetate with 6percent net retention of configuration.The results are discussed in terms of successive ion pairs and carboxyl inversion product arising early on the reaction path and other products later.