Thermal Unimolecular Decomposition of Bicyclopropyl and Deuterated Analogues: Infrared Photoactivation as a Diagnostic Tool in Mechanistic Organic Chemistry

Article abstract of DOI:10.1021/jo00146a006

The infrared photochemistry of bicyclopropyl yields product mixtures that are not easily rationalized on the basis of the mechanistic scheme suggested by previous pyrolysis work.As a result of this inconsistency the thermal chemistry of bicyclopropyl and analogues deuterated specifically on one ring has been reexamined.A significant new reaction channel involving the chemically activated decomposition of cyclohexene to ethylene and butadiene has been demonstrated.Evidence for the involvement of chemically activated cyclohexene is as follows: (1) isotopic labelingstudies implying a symmetric intermediate, (2) a pressure-dependent ratio of cyclohexene to butadiene and ethylene, (3) good agreement between experimental and calculated values for the unimolecular rate constant for retro-Diels-Alder decay of hot cyclohexene.A comprehensive mechanism for the unimolecular decay of bicyclopropyl is proposed.The important elements of this mechanism are a single first-formed 1,3 biradical common to all products and the intervention of chemical activation in the generation of several of the secondary products.