Please use this identifier to cite or link to this item:
http://hdl.handle.net/11375/20818
Title: | The Question of Nonclassical Free Radicals: Decomposition of T-Butyl 7-Norbornene- and Norbornane- Percarboxylates |
Authors: | Zador, Eugene |
Advisor: | Warkentin, J. |
Department: | Chemistry |
Keywords: | nonclassical, free radicals, decomposition, percarboxylates, reaction |
Publication Date: | May-1967 |
Abstract: | <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> |
URI: | http://hdl.handle.net/11375/20818 |
Appears in Collections: | Digitized Open Access Dissertations and Theses |
Files in This Item:
File | Description | Size | Format | |
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Zador_Eugene_1967May_Ph.D..pdf | 2.87 MB | Adobe PDF | View/Open |
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