Many aspects of the desulfurization of trisulfides have been investigated. Efforts directed toward the syntheses of cyclic trisulfides provided mixtures of oligomers or the corresponding disulfide. Radiochemically labelled trisulfides and an optically active trisulfide have been desulfurized by a variety of phosphines. Triarylphosphines preferentially removed the central sulfur atom under all conditions, while tris(dialkylamino)phosphines exhibited preferential terminal sulfur removal in low polarity solvent with a trend to increased central sulfur removal with increased solvent polarity. Exchange phenomena were examined and a mechanistic rationalization presented. Desulfurization by triarylphosphines was concluded to proceed by the rate-determining decomposition of a phosphonium salt to form products, while desulfurization by tris(dialkylamino)phosphines was considered to have phosphonium salt formation as the rate-determining step. / The reaction of trisulfides with trialkyl phosphites to give a mixture of unsymmetrical and symmetrical disulfides has been studied. Mechanistic and synthetic aspects are described. / The spontaneous desulfurization of sulfenic sulfonic thioanhydrides and exchange of the thiosulfonate products in polar solvents were examined.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.68520 |
| Date | January 1979 |
| Creators | Smith, Roger Astbury. |
| 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: 000090103, proquestno: AAINK50567, Theses scanned by UMI/ProQuest. |
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