A general synthesis for bridged bicyclic disulfide compounds was refined and expanded from (3.2.1) to (4.2.1) and (2.2.1) systems. Various derivatives were synthesized through modification of the hydroxyl functionality in these molecules. The oxidation of all bridged bicyclic disulfide compounds to their corresponding bridged bicyclic thiosulfinate esters (a previously unknown class of compounds) was performed. Three crystal structures were obtained and selected bond lengths, bond angles and torsion angles were compared with the calculated values obtained using MMX molecular mechanics via the PCMODEL program. / The m-CPBA oxidation of the above bridged bicyclic thiosulfinate esters was followed at low temperature using $ sp1$H and $ sp{13}$C NMR spectroscopy. $ alpha$-Disulfoxides were detected as the first intermediates in this oxidation process and were seen at temperatures and concentrations greater than any previously reported. Strong evidence was also found to suggest the intermediacy of O,S-sulfenyl sulfinates. A clear mechanistic proposal for the rearrangement of bridged bicyclic $ alpha$-disulfoxides to their corresponding thiosulfonate esters was presented based on experimental results. / Attempts towards the synthesis of the bridged bicyclic disulfide analogue of ergosterol peroxide using diatomic sulfur methodologies were reported. These attempts were not successful. / The generation of the pseudo-diatomic species, R-P = S (thioxophosphanes), using a methodology previously developed in our laboratory was examined. The thioxophosphanes (R = C$ sb6$H$ sb5$, C$ sb2$H$ sb5$ and p-Cl-C$ sb6$H$ sb4$) were trapped with 1,3-dienes to give cyclic and bridged bicyclic thiophosphoranes.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.39272 |
| Date | January 1991 |
| Creators | Folkins, Patricia L. (Patricia Lorna) |
| 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: 001257693, proquestno: NN72168, Theses scanned by UMI/ProQuest. |
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