37998-83-7Relevant articles and documents
Application of EPR spectroscopy to the determination of the rates of reaction and selectivity of attack of the tert-butoxyl radical on esters: the interplay of electronic, polar, steric and stereoelectronic factors
Bennett, John E.,Gilbert, Bruce C.,Lawrence, Sara,Whitwood, Adrian C.,Holmes, Andrew J.
, p. 1789 - 1796 (2007/10/03)
Rate constants have been determined by steady-state EPR spectroscopy experiments for hydrogen-atom abstraction by ButO radical from a variety of esters.The values, which range over two orders of magnitude (5 * 103-5 * 105 dm3 mol-1 s-1 at ca. 300 K) are significantly lower than those for related ketones and ethers and reflect, at least in part, the importance of the appropriate C-H bond dissociation energies and the stabilization of carbonyl-conjugated radicals.The relative lack of reactivity of C-H bonds in unsubstituted five-membered rings is believed to reflect ring-strain in the derived radicals; possible stereoelectronic effects are discussed.
