<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)
| Identifer | oai:union.ndltd.org:mcmaster.ca/oai:macsphere.mcmaster.ca:11375/20818 |
| Date | 05 1900 |
| Creators | Zador, Eugene |
| Contributors | Warkentin, J., Chemistry |
| Source Sets | McMaster University |
| Language | en_US |
| Detected Language | English |
| Type | Thesis |
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