Ph.D. / The research described in this thesis was directed at advancing the application of metal triflates, Al(OTf)3 in particular, in organic synthesis, on the one hand and to contribute to the understanding of the underlying basis for their catalytic activity. The study was undertaken against the background and on the bases of a detailed literature study of metal triflates, their chemical and catalytic properties and applications thereof. Amongst others, it deals with the possible role of metal-bound water that give rise to Brønsted type acidity and that this induced Brønsted acidity may be responsible for the catalytic activity that is observed. The study was prompted by the realisation that Al(OTf)3 was largely neglected as a potential reusable catalyst. This is in marked contrast to the attention paid to other metal triflates, the rare earth metals in particular. Earlier work in this laboratory has shown that Al(OTf)3 is stable in water from which it can be recovered easily for reuse. In addition it showed promise as a Lewis acid catalyst and is relatively soluble in several organic solvents. New applications for the use of Al(OTf)3 have now been demonstrated. These include the efficient formation of acetals from aldehydes and ketones. The conversions can be carried out in an alcohol/orthoester mixture or preferably in neat orthoester. Other metal triflates, notably Sc(OTf)3 and In(OTf)3, are useful alternative catalysts. Al(OTf)3 can be easily recycled without loss of activity. This methodology also can be applied to aldehydes and ketones containing TBDMS groups without effecting deprotection of the ethers. In view of the sensitivity of the TBDMS groups to hydrolysis in the presence of triflic acid the results suggest little hydrolysis (or alcoholysis) of the metal triflates in the protic solvents used, which would generate trifluoromethanesulfonic acid as a consequence of such metal based hydrolysis. Al(OTf)3 was also found to be a good catalyst for the formation of THP ethers. It proved to be excellent for Friedel Crafts reactions using alkynes as substrates. Al(OTf)3 together with other triflates offers a mild alternative to the more traditional water sensitive Lewis acids, e.g. BF3, AlCl3 and TiCl4, which are difficult to recover and require the use of extremely dry solvents.

M.Sc. (Chemistry) / The quality of fresh water is deteriorating due to pollution by a wide range of substances as a result of industrial, agricultural, domestic, mining and other anthropogenic activities. Even at trace levels in water, some pollutants are toxic to organisms through acute or chronic effects or through bioaccumulation. Conventional water treatment is often ineffective at removing pollutants to the ultra-low levels required by water quality standards and other technologies employed to remove toxic compounds from water have high capital and operating costs and other disadvantages. There is therefore an ongoing need to develop low-cost technologies that are effective for the removal of toxic pollutants from water. In our laboratories, iron and nickel (Fe/Ni) decorated carbon nanotube (CNT)/cyclodextrin polymers (β-CDs) showed promising results in previous studies carried out for the degradation and removal of toxic organic pollutants in water. However, the powder form of the polymer makes its direct application in water treatment difficult. The leaching of metal nanoparticles and carbon nanotubes from the polymer into the water being treated is also of concern due to their potential toxicity. In this study, alginate beads were investigated as supports for two kinds of nanocomposites, Fe/Ni decorated carbon nanotubes and Fe/Ni decorated carbon nanotube/cyclodextrin polymers. Alginate beads were selected as supports to render the nanocomposites more conducive towards water treatment applications since they are easy to handle and recover from water and are also stable supports that can prevent the leaching of nanomaterials into treated water.

D.Phil. (Chemistry) / Please refer to full text to view abstract

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The present investigation has involved a kinetic and mechanistic study of the thermal cyclization of 3-acetoxy-3-(2-pyridyl)-2-methylenepropanoate esters and related compounds to 2-substituted indolizines. Substrates for the kinetic study were prepared via the Baylis-Hillmann reaction of pyridine-2-carboxaldehydes with acrylate esters, acrylonitrile and methyl vinyl ketone. The resulting hydroxy compounds were then acetylated to afford the acetoxy derivatives, thermal cyclization of which gave the corresponding 2-substituted indolizines. The cyclization reactions was followed using 'H NMR spectroscopy and were shown to follow firstorder kinetics. The influence of the various substituents on the observed first-order rate constants has been examined and variable temperature studies have permitted evaluation of activation parameters for the formation of methyl indolizine-2-carboxylate and ethyl indolizine-2-carboxylate. An alternative route to 2-substituted indolizines via halogenated derivatives was explored and several halogenated 2-pyridyl derivatives were synthesised and their thermal cyclization to indolizines was attempted. Novel 5-methylindolizine-2-carboxamides were prepared as part of this investigation and dynamic NMR spectroscopy was used to study internal rotation about the amide N-CO bond in these compounds.

Several camphor and pinane derivatives have been synthesised and evaluated for use as chiral auxiliaries in asymmetric synthesis. Various blocking groups have been attached to the camphor skeleton in attempts to improve stereofacial selectivity; these include α-methoxybenzyl and xylyl groups, and novel stereoisomeric ketal moieties derived from meso- and (R,R)-(-)-2,3-butanediol. Benzylation reactions carried out on the lithium enolates of ester derivatives of the camphor-derived chiral auxiliaries afforded α-benzylated products in 5-60% diastereomeric excess. Stereochemical aspects have been explored using high resolution NMR, X-ray crystallographic and computer modelling techniques, and hydrolysis of selected α-benzylated products has permitted the diasteroselective bias to be confirmed. Opposite configurations at the new stereogenic centre are clearly favoured by the xylyl and ketal blocking groups - an observation rationalised in terms of the presence or absence of chelating potential in the blocking group. Baylis-Hillman reactions carried out on a series of specially prepared camphor-derived acrylic esters containing the ketal blocking group exhibited both low diastereoselectivities (0-30% d.e.) and very long reaction times. Chiral silyl enol ethers, synthesised using both pinane and camphor derivatives as chiral auxiliaries, showed up to 20% diastereomeric excess in MCPBA oxidation, alkylation and Mukaiyama reactions. Attempts to bring the prochiral centre in the silyl enol ether substrates closer to the chiral auxiliary, and thus improve the stereofacial selectivity, proved unsuccessful. The silyl enol ether derivatives, however, display interesting fragmentation patterns in their electron impact mass spectra, which were investigated using a combination of high resolution MS, comparative low resolution MS and metastable peak analysis.

Solar evaporite systems are man-managed ecosystems which are highly vulnerable to biological,physical and chemical disturbances. The problems encountered in such systems are in many cases found to be associated with the microbial ecology and the design of the system. This project focussed on investigating the nature of organic compounds contaminating soda ash produced at a solar evaporite production system located at Sua Pan in Botswana. Several years after the plant was commissioned, problems, including accumulation of total organic carbon (TOC) and discolouration of the soda ash product were encountered. The salt produced also retained high moisture content and was coloured pink. These phenomena impacted severely on the economic performance of the enterprise. This study was aimed at determining the origin and fate of these organic compounds within the system in order to elucidate the nature of the problem and also to conceptualise a remediation strategy suitable to reducing its impact. This was achieved by analysis of both dialysed and solvent extracts of the influent brine (well-brine), brine in the ponds (T-brine) and the bicarbonate filter cake. Although complete identification of the organic compounds isolated was not undertaken in this study, spectroscopic analysis of compounds isolated, by UV, IR, NMR and MS, strongly indicated that fulvic acids, a component of the influent well-brine organics, contribute to the organic contamination of the final product. Part of this component, however, is degraded during the ponding process. It was shown that an extracellular polysaccharide (EPS) produced by Dunaliella. spp., which proliferates in the evaporation ponds, contributes in a major way to the accumulation of TOC in the system. This was demonstrated by relating the sugar profile of carbohydrates isolated from the pond brine and final product, being arabinose, xylose, 2-o-methyl hexose, mannose, glucose and galactose. Studies reported show that EPS production was enhanced when algal cultures were exposed to stress conditions of high illumination, increasing salinity and temperature, and nitrogen limitation. Studies undertaken for the development of a remediation process for this system have shown that nutrient stripping and bacterial systems could be applied to deal with the dissolved TOC fraction, whereas adsorption systems could deal with the particulate fractions. Algal systems showed most potential for the removal of nutrients in the influent well-brine compared to chemical processes.Complete removal of ammonium and phosphorus removal efficiencies of pproximately 50% were achieved in an unoptimised pilot-scale Dunaliella-based HRAP. While similar effects were demonstrated for chemical processes, some economic constraints were noted. The potential of halophilic bacterial systems for the degradation of organic compounds in brine was also demonstrated. The limitations on the performance of such systems, associated with the low metabolic diversity, and poor immobilisation of physico-chemical processes were found to have a very low impact on the dissolved TOC fraction of the brine, the removal of the particulate material was found to result in a 35% TOC reduction in the final soda ash product and the production of a white final product.halobacteria, however, were noted. Although physico-chemical processes were found to have a very low impact on the dissolved TOC fraction of the brine, the removal of the particulate material was found to result in a 35% TOC reduction in the final soda ash product and the production of a white final product. Apart from a description of the microbial ecology of the ponds and the identification of major contributions to the TOC of the final product, a number of remediation strategies were evaluated and are described. These include chemical and biological stripping of nutrients sustaining microbial TOC production in the ponds, and also biological and physico-chemical processes for their removal once formed. Future studies to undertake the further development of these proposals has been described

The concept of combining two well established areas of organic chemistry, viz., organosilicon chemistry and the use of chiral auxiliaries, into a viable, alternative method of asymmetric synthesis has only very recently begun to receive attention. At the outset of this investigation, no asymmetric reactions of silyl enol ethers, chiral by virtue of optically active substituents on the silicon, had been reported. A range of novel chiral silyl enol ethers have thus been prepared from a variety of ketones, including pinacolone, cyclohexanone, and α-tetralone, and employing menthol, borneol, and cholesterol as chiral auxiliaries. These preparations have been achieved via several distinct routes, including a novel convergent approach involving the isolation of either the chloro(menthyloxy)dimethylsilane or the (bornyloxy)chlorodimethylsilane. The MS and NMR spectra of these silyl enol ethers were examined in detail and, in the case of the crystalline cholesteryloxy silyl enol ether, the X-ray structure has been determined. The potential of chloroalkoxysilanes to act as general, chiral derivatizing agents has been established by the preparation of diastereomeric silyl acetal mixtures of racemic secondary alcohols (e.g. I-phenylethanol and 2-octanol). The experimental diastereomeric ratios, obtained by GLC and ¹H NMR spectroscopy, approached the expected value of unity, confirming the potential of the alkoxychlorosilanes as chiral probes. The chiral silyl enol ethers have been successfully oxidized to the corresponding α-siloxy ketones employing MCPBA, MMPP, and 2-(phenylsulphonyl)-3-phenyloxaziridine as oxidizing agents and the diastereomeric excesses obtained, which varied from 0 to 16%, indicated some potential for stereochemical control. Alkylation and hydroxyalkylation reactions of the silyl enol ethers have yielded the expected α-iert-butyl and β-hydroxy ketones in good to excellent material yields, with the enantiomeric excesses, as determined by chiral shift reagent studies, reaching 14%. To improve the stereo control in these reactions, attempts have been made to prepare chiral silyl enol ethers with auxiliaries possessing the potential for transition state complex co-ordination in the reactions under consideration. The preparation of such silyl enol ethers, incorporating the proline-derived auxiliaries, N-methyl-2-hydroxymethylpyrrolidine and 2-methoxymethylpyrrolidine met with only limited success. In an alternative approach, three derivatives of 2,3-dihydroxybornane have been prepared. However, two of these auxiliaries, viz., 3-exo-benzyloxy-2-exo-hydroxybornane and 3-exo-(1-methoxyethoxy)-2-exo-hydroxybornane failed to form silyl enol ethers, even under considerably more vigorous conditions than normally employed. The third derivative, 3,3-ethylenedioxy-2-hydroxybornane has been successfully utilized in the preparation of a pinacolone-derived chiral silyl enol ether. Hydroxyalkylation of this compound with benzaldehyde has yielded the β-hydroxyketone with significantly improved enantiomeric excess (26%) and a transition state complex has been proposed to rationalize this improvement.