Photochemical generation and absolute reactivity of an allene oxide in solution.
A method for the rapid photochemical generation of allene oxides is described that allows absolute rate constants for the reactions of these interesting reactive intermediates to be measured. The fluorenylideneallene oxide generated using this method was found to rearrange to the corresponding cyclopropanone with a rate constant of 0.0012 s(-1) in TFE. The lifetime of the allene oxide was significantly reduced in the presence of nucleophiles such as halides, methanol, and water. [reaction: see text]
Clay
M D
MD
Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, Canada B3H 4J3.
Durber
J
J
Schepp
N P
NP