The selective oxidation of alcohols to the corresponding carbonyl product is an important transformation. Traditionally this reaction has been carried out using stoichiometric oxidants, but such methods are highly undesirable from an environmental viewpoint. In the fine chemical and pharmaceutical industries, oxidative transformations prove problematic, and are often avoided, due to a limited number of existing chemoselective and sustainable oxidation methods. The demand for new, environmentally sustainable and efficient alcohol oxidation methods has driven academic research, and a number of systems have emerged which employ catalytic metal loadings with oxygen as the terminal oxidant. In terms of sustainability, oxygen is the ideal oxidant as it is abundant, and water is the only byproduct formed during aerobic alcohol oxidation catalysis. In spite of the progress made in recent years, the introduction of such systems into industrial processes has not occurred. The aim of this thesis is the development of sustainable and industrially viable catalyst systems for aerobic alcohol oxidation. The research reported in this thesis studies two different catalytic systems. Firstly, the combination of nitroxyl radicals with copper complexes was explored (Chapter 2). The substrate scope was studied, using different nitroxyl radicals, exploring the effect of steric hindrance. The influence of mass transfer and gas pressure was also examined, in order to more efficiently utilise these expensive nitroxyl radicals. In Chapters 3 and 4, research was focused on a zeolite encaged 1,10-phenanthroline-Pd(NO3)2 catalyst system. The aim of these studies was to develop a stable Pd(ll) catalyst which would exhibit longer lifetimes compared to homogeneous systems.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:709812 |
| Date | January 2016 |
| Creators | Rogan, Luke |
| Publisher | Queen's University Belfast |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
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