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The Question of Nonclassical Free Radicals: Decomposition of T-Butyl 7-Norbornene- and Norbornane- Percarboxylates

<p> There is only one unambiguous report in the literature of anchimeric assistance by the π-bond in a free radical reaction. It was the purpose of this work to investigate the possibility of such acceleration in the thermal homolysis of 7-norbornene peresters. Two such t-butyl peresters, the isomeric syn- and anti-7-norbornene percarboxylates as well as t-butyl
7-norbornane percarboxylate, were prepared and their decomposition was studied by kinetic methods and product analysis.</p> <p> The homolysis of 7-norbornene peresters is shown to
occur with rate-determining perester O-O bond rupture, the transition state of which may be a hybrid of radical and polar structures. A low order of anchimeric acceleration may also assist the decomposition of the syn compound.</p> <p> The pKa values for syn- and anti- 7-norbornene- and 7-norbornane- carboxylic acid are reported.</p> / Thesis / Doctor of Philosophy (PhD)

Identiferoai:union.ndltd.org:mcmaster.ca/oai:macsphere.mcmaster.ca:11375/20818
Date05 1900
CreatorsZador, Eugene
ContributorsWarkentin, J., Chemistry
Source SetsMcMaster University
Languageen_US
Detected LanguageEnglish
TypeThesis

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