The investigation has been focussed on the synthesis and characterisation of camphor-derived chiral auxiliaries that incorporate two camphor skeletons and an evaluation of their stereodirecting potential in ester α-benzylation reactions. Two regioisomeric camphorquinone-derived monoketals were synthesised and identified by 1D- and 2D-NMR, and X-ray crystallography. The stereo-directing potential of the alcohols that resulted from reduction of these ketones as chiral auxiliaries in the alkylation of carboxylate ester derivatives has been studied. The diastereoselectivities shown by NMR spectroscopy range from 14- 30 % d.e. for (1R,2 S, 3R) -2 ,2-[ (1R, 2 S, 3R) -bornane-2,3-dioxy] - bornan-3-ol and 68-74 % d.e. for (1R, 2S ,3R) -3 ,3-[ (1R, 2S ,3R) - bornane-2, 3 -dioxy]bornan-2-ol with selectivities that correlate with the size of the alkyl group in the ester moiety. Trapping of the enolates generated from (1R, 2S ,3R)-2, 2 -[(1R,2 S, 3R) -bornane- 2,3-dioxy]bornan-3-yl propanoate afforded both E- and Z-silyl ketene acetal derivatives in the ratio of 64:36 confirming the formation of both possible enolate structures during enolization. Chiral auxiliaries containing a hemiaminal ether blocking group as well as two chiral alcohols containing monothio-ketal blocking groups have also been synthesised. α-Benzylation of their corresponding propanoate esters afforded the alkylated product with disappointingly low diastereos electivities. Asymmetric reduction of α-keto esters attached to (1R, 2 S, 3R) - 2,2- [ (1R,2 S, 3R) -bornane-2, 3 -dioxy]bornan-3-ol and (1R, 2S ,3R) - 3,3- [ (1R,2 S, 3R) -bornane-2, 3 -dioxy]bornan-2-ol with metal hydrides proceeded with selectivities of up to 30 % d.e. Modelling of the keto ester derivatives at DFT levels provided useful insights into possible conformations adopted by the two α-keto esters and hence the preferred face of attack by metal hydride during reduction.

No abstract was provided. / Thesis / Master of Engineering (ME)

No description available.

No description available.

No description available.

La tesis doctoral está dividida en una introducción general y cuatro capítulos. En la introducción general, se describen diferentes productos naturales y derivados sintéticos que contienen un núcleo de oxindol en su estructura junto a comentarios sobre sus actividades biológicas. Además, también están incluidas diversas metodologías de síntesis para la síntesis de estos derivados de oxindol junto a una explicación general sobre el proceso de alquilación desacetilativa. Los capítulos se han desarrollado con una breve introducción, una propuesta de objetivos, comentarios y discusión de los resultados obtenidos en las investigaciones finalizando con las conclusiones obtenidas. El Capítulo 1 trata sobre la síntesis de 2-oxindoles 3,3-disustitutidos a través de un proceso de alquilación desacetilativa utilizando halogenuros de alquilo. El Capítulo 2 describe la alilación y la alilación desacetilativa catalizada por paladio de los derivados de 2-oxindol utilizando alcoholes alílicos no activados. En el Capítulo 3 está incluida la síntesis de 3-fluoro-2-oxindoles combinando las metodologías descritas en los dos anteriores capítulos. Finalmente, en el Capítulo 4, se desarrolla la alquilación fotocatalizada de olefinas electrofílicas a través de sulfinatos de zinc bencílicos y alquílicos.

This study concerned the synthesis of modified terephthalic acid monomers and branched dialcohols for the synthesis of polyesters with different properties. Monomers were prepared by esterification of terephthalic acid (TPA) and the alkylation of the ester dimethyl terephthalate (DMT). If alkylation was unsucessful, TPA was brominated using N-bromosuccinimide (NBS) and other brominating agents. However, the bromination reactions were also unsuccessful. Therefore, oxidation reactions of 2-bromoparaxylene were conducted as an attempt to obtain the desired monomers, however a mixture of products was produced that were difficult to separate. Subsequently, the brominated TPA was bought, and the alkylation reactions were performed using tetramethyltin and other alkylating agents; however the alkylation reaction was once again unsuccessful. Despite the difficulties encountered during monomer synthesis, polymerization of the obtained monomers was investigated. Polymer synthesised by the technique of condensation polymerization of branched diols and the brominated TPA. The unbranched diol monomers and unsubstituted DMT were used to synthesize reference polymers for comparison with the novel polymers produced in this study. The following diols were used: 1,2-propanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol. A batch reactor equipped with a mechanical stirrer connected to the vacuum pump was used as polymerization vessel. The polyesters were synthesised and they were characterised using IR and NMR. Additional polymer analysis was performed using Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), X-Ray Diffraction (XRD), Gel permeation Chromatography (GPC) and Scanning Electron Microscopy (SEM). The results of the analyses indicated that the polymers became flexible and softer with an increasing number of methylene units in the main chain. Consequently, the melting point of the polymer decreased when there was branching present. SEM analyses showed that polymers were softer and had no hard edges, and the SEM also showed the catalyst inside the polymers. The decomposition temperature changed very slightly with alkyl substitution or the presence of bromide in benzene ring. It was concluded that the benzene ring did not become activated as a number of methods were attempted unsuccessfully to facilitate reaction by either alkylation or bromination. The methyl branches on the diols were not held responsible for any changes in the properties of the polyesters. Bromination of the monomers resulted in polymers that were structurally amorphous and that demonstrated a low tensile strength. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2015

This study concerned the synthesis of modified terephthalic acid monomers and branched dialcohols for the synthesis of polyesters with different properties. Monomers were prepared by esterification of terephthalic acid (TPA) and the alkylation of the ester dimethyl terephthalate (DMT). If alkylation was unsucessful, TPA was brominated using N-bromosuccinimide (NBS) and other brominating agents. However, the bromination reactions were also unsuccessful. Therefore, oxidation reactions of 2-bromoparaxylene were conducted as an attempt to obtain the desired monomers, however a mixture of products was produced that were difficult to separate. Subsequently, the brominated TPA was bought, and the alkylation reactions were performed using tetramethyltin and other alkylating agents; however the alkylation reaction was once again unsuccessful. Despite the difficulties encountered during monomer synthesis, polymerization of the obtained monomers was investigated. Polymer synthesised by the technique of condensation polymerization of branched diols and the brominated TPA. The unbranched diol monomers and unsubstituted DMT were used to synthesize reference polymers for comparison with the novel polymers produced in this study. The following diols were used: 1,2-propanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol. A batch reactor equipped with a mechanical stirrer connected to the vacuum pump was used as polymerization vessel. The polyesters were synthesised and they were characterised using IR and NMR. Additional polymer analysis was performed using Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), X-Ray Diffraction (XRD), Gel permeation Chromatography (GPC) and Scanning Electron Microscopy (SEM). The results of the analyses indicated that the polymers became flexible and softer with an increasing number of methylene units in the main chain. Consequently, the melting point of the polymer decreased when there was branching present. SEM analyses showed that polymers were softer and had no hard edges, and the SEM also showed the catalyst inside the polymers. The decomposition temperature changed very slightly with alkyl substitution or the presence of bromide in benzene ring. It was concluded that the benzene ring did not become activated as a number of methods were attempted unsuccessfully to facilitate reaction by either alkylation or bromination. The methyl branches on the diols were not held responsible for any changes in the properties of the polyesters. Bromination of the monomers resulted in polymers that were structurally amorphous and that demonstrated a low tensile strength. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2015

No description available.

The final objective of this project is to create an environmentally friendly solid alkylation catalyst to replace the commercially available liquid acid catalysts, such as hydrofluoric acid and sulfuric acid, which are used in the petroleum industry. My research target is to synthesize the diazonium PFSI zwitterions, which can be chemically grafted on the silica as the solid alkylation catalyst. A 4-steps synthesis is designed to prepare the diazonium PFSI zwitterions. The first two steps were successfully completed in the lab. The first one is to prepare the starting material of 4-nitrobenzenesulfonamide from an ammonolysis reaction between 4-nitrobenzene sulfonyl chloride and ammonium hydroxide. And next, a base catalyzed coupling reaction was carried out with 4-nitrobenzenesulfonamide and commercially available perfluorobutane sulfonyl fluoride with nitrogen gas (N2) protection. The coupling product (I in Figure 1) was then purified by extraction and recrystallization. All chemicals in the synthesis procedure were characterized with proton NMR, fluorine NMR, Infrared (IR) spectroscopy and melting points.