A series of hindered biphenols specifically designed to form stable biphenoxy radicals were prepared by an oxidative coupling reaction of hindered phenols in the presence of CuCl and molecular oxygen in butyronitrile or by reacting the diphenoquinones with HCl gas. / The biphenoxy radicals generated from the oxidation of the original biphenols with an aqueous solution of KOH/K$ sb3$Fe(CN)$ sb6$ or Ag$ sb2$O were used as reagents in organic reactions and catalysts in the oxidation of diarylmethanes to corresponding ketones. They were also used in the synthesis of novel ether and acetal monomers through a quantitative radical coupling reaction with monomers containing activated methylene groups. These ether and acetal compounds were readily cleaved under acidic conditions thus providing a new method of cleaving benzylic and t-butyl ethers under mild conditions and for functionalizing activated methylene groups. To simplify the purification steps biphenol A6.19 was incorporated into the backbone of a poly(aryl ether) chain and used as a polymeric support material. / The quantitative radical coupling reaction and cleavage of the resulting ethers and acetals led to the synthesis of novel carbon - oxygen coupled polymers that could potentially be used as photoresist materials since they are cleaved to low molecular weight organic compounds in the presence of acid. / In part B a new mass spectrometry technique, Matrix Assisted Laser Desorption Ionization-Time of Flight, was examined as a potential tool in determining the absolute molecular weight, sequence distribution, and end groups of low molecular weight polydisperse polymers and cyclic oligomers.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.41975 |
| Date | January 1997 |
| Creators | Barbiero, Gennaro. |
| Contributors | Hay, A. S. (advisor) |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Doctor of Philosophy (Department of Chemistry.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 001566632, proquestno: NQ29884, Theses scanned by UMI/ProQuest. |
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