Unprecedented Reactivity of Fluorocarbons and the Synthesis of New Inclusion Compounds

Organic chemistry

Robertson, Colin Dick

University:University of Glasgow

关键词: Organic chemistry;   

Others  :  http://theses.gla.ac.uk/78220/1/11007612.pdf

来源: University of Glasgow

【 摘 要 】

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.