The behavior of biphenyl and naphthyl sulfinate and sulfoxylate esters under flash vacuum thermolytic and photolytic conditions was studied and a new tetrasubstituted dihydrophenanthrene was isolated. Several, 2,2'-biphenyl diols were synthesized including some with specifically deuterated alkyl chains. These diols were cyclized to give symmetrically substituted as well as cis-/trans- unsymmetrically substituted dibenzoxepins. The dynamic NMR properties of these dibenzoxepins were studied and the free energy barriers of conformational inversion were measured and related to the steric interactions of the alkyl substituents. The preferred conformations of the trans-dibenzoxepins were related to the relative stabilities of the alkyl substituents in the axial or equatorial position. The reaction of the 2,2'-biphenyl diols with trimethylsilylbromide yielded diolefinic biphenyls. In some other cases rearrangements to cyclized products were observed. The photolytic cyclization of the diolefinic biphenyls resulted in new tetrasubstituted tetrahydropyrenes and pyrenes.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.77156 |
| Date | January 1981 |
| Creators | Mullins, Dennis F. |
| 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: 000138854, proquestno: AAINK58129, Theses scanned by UMI/ProQuest. |
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