Unprecedented Reactivity of Fluorocarbons and the Synthesis of New Inclusion Compounds

Robertson, Colin Dick (1990) Unprecedented Reactivity of Fluorocarbons and the Synthesis of New Inclusion Compounds. PhD thesis, University of Glasgow.

Abstract

A new and unprecedented reactivity of saturated fluorocarbons has been discovered. Application of this reaction to perfluorodecalin at ambient temperature and above is used to synthesis members of the 'octa-host' series. The mechanism of the reaction and its extension to analogous reactions, including different substrates (unsaturated fluorocarbons or other saturated fluorocarbons, particularly those with a tertiary carbon centre) and different nucleophiles is investigated. A Single Electron Transfer (SET) pathway is favoured. The 'octa-host' series itself, an extension of the 'hexa-host' series, is further investigated and new host inclusion discovered. A new class of host materials, octakis(aryloxy)naphthalenes, is synthesised. Structural investigation of six octa-hosts by X-ray single-crystal diffraction is used to elucidate their inclusion properties; uniquely one of the octa-hosts, octakis(m-tolylthio)-naphthalene has a 'clathrate' open-packed structure as a non-solvate, with no stabilisation other than by van der Waals forces . Another, octakis(cyclohexylthio)naphthalene, contains an axial C-S cyclohexyl bond conformation. These two solid-structures are also investigated by magic angle spinning solid state n.m.r. Other 'octa-host'-like variants were investigated, including routes to 'deca-hosts', anthracene based systems, both through classical synthesis routes and using the newly discovered reactivity of saturated fluorocarbons. More structural tuning of the 'hexa-'host' concept was investigated by the synthesis and solid-state structure elucidation of hexakis -(p-hydroxyphenyloxy) benzene, a potential beta-Hydroquinone analogue. Chiral legs for 'hexa-' and 'octa-hosts' were briefly investigated. The role of symmetry in partnership with molecular conformation and shape is analysed for the 'octa-hosts', C2 equivalents of the C3 'hexa-hosts', and general principles discussed. Fluorocarbon chemistry is summarised and recent progress in the directed design of inclusion compounds reviewed.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Organic chemistry
• Date of Award: 1990
• Depositing User: Enlighten Team
• Unique ID: glathesis:1990-78220
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 30 Jan 2020 15:36
• Last Modified: 30 Jan 2020 15:36
• URI: https://theses.gla.ac.uk/id/eprint/78220