Carbonylation of cyclohexene with carbon dioxide (CO2) using transition metals as heterogeneous and homogeneous catalysts
- Authors: Sekaleli, Bafokeng Thabelo
- Date: 2024-10-11
- Subjects: Uncatalogued
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/464565 , vital:76522
- Description: From a green chemistry perspective, carbon dioxide (CO2) emerges as an appealing C1 synthon, given its abundance in the atmosphere and cost-effectiveness. Many essential chemicals for daily life are derived from fossilized carbon sources like coal, petroleum, and natural gas. However, the by-product of these processes, CO2, poses environmental risks when excessively emitted as a greenhouse gas. Achieving a balance between carbon emissions and removal is crucial to address environmental concerns surrounding CO2. Utilizing CO2 as a C1 source in organic synthesis holds promise for mitigating this balance in the long term. Combining CO2 with other underutilized fine chemicals, such as alkanes, alkenes, and alkynes, to produce more valuable platform chemicals presents an economically viable strategy due to carbon dioxide’s abundance, low cost, and recyclability. Despite its simplicity, CO2's high thermodynamic stability and low kinetic reactivity, owing to its highly oxidized state, pose challenges to its use as a feedstock. Overcoming these hurdles requires catalysts to enhance CO2 reactivity. Our work focuses on developing and employing catalytic systems capable of activating CO2 as a C1 synthon in reactions with cyclohexene and a reducing agent to yield carboxylic acids or esters. In one approach, we have developed heterogeneous catalyst systems comprising transition metals (Au, Fe, Ni, Ru) supported on metal oxide (TiO2). Characterization techniques such as TEM, EDX, UV-Vis, BET, and XRD were used to study the properties of these materials. The catalysts were evaluated in a reaction involving cyclohexene, CO2, and H2O. In another approach, we explored the use of cyclo-tris(tetracarbonylruthenium) [Ru3(CO)12] as a homogeneous catalyst in a reaction involving cyclohexene, methanol, and CO2 in the presence of an ionic liquid, 1-Butyl-3-methylimidazolium chloride ([BMIM]+Cl-). 1H NMR and ATR-FT-IR were utilized to characterize [BMIM]+Cl-. The reaction product was characterised utilizing GC-MS. Upon seeing that Ru3(CO)12 changes color from orange to black when exposed to heat, an investigation was undertaken on the kind of transformations that the catalyst undergoes. This investigation was carried out with the hopes of finding the structures that could be resulting from Ru3(CO)12 during the reaction and their significance to it. The orange and black Ru complexes were characterized utilizing DSC, TGA, ATR-FT-IR and PXRD. , Thesis (MSc) -- Faculty of Science, Chemistry, 2024
- Full Text:
- Date Issued: 2024-10-11
- Authors: Sekaleli, Bafokeng Thabelo
- Date: 2024-10-11
- Subjects: Uncatalogued
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/464565 , vital:76522
- Description: From a green chemistry perspective, carbon dioxide (CO2) emerges as an appealing C1 synthon, given its abundance in the atmosphere and cost-effectiveness. Many essential chemicals for daily life are derived from fossilized carbon sources like coal, petroleum, and natural gas. However, the by-product of these processes, CO2, poses environmental risks when excessively emitted as a greenhouse gas. Achieving a balance between carbon emissions and removal is crucial to address environmental concerns surrounding CO2. Utilizing CO2 as a C1 source in organic synthesis holds promise for mitigating this balance in the long term. Combining CO2 with other underutilized fine chemicals, such as alkanes, alkenes, and alkynes, to produce more valuable platform chemicals presents an economically viable strategy due to carbon dioxide’s abundance, low cost, and recyclability. Despite its simplicity, CO2's high thermodynamic stability and low kinetic reactivity, owing to its highly oxidized state, pose challenges to its use as a feedstock. Overcoming these hurdles requires catalysts to enhance CO2 reactivity. Our work focuses on developing and employing catalytic systems capable of activating CO2 as a C1 synthon in reactions with cyclohexene and a reducing agent to yield carboxylic acids or esters. In one approach, we have developed heterogeneous catalyst systems comprising transition metals (Au, Fe, Ni, Ru) supported on metal oxide (TiO2). Characterization techniques such as TEM, EDX, UV-Vis, BET, and XRD were used to study the properties of these materials. The catalysts were evaluated in a reaction involving cyclohexene, CO2, and H2O. In another approach, we explored the use of cyclo-tris(tetracarbonylruthenium) [Ru3(CO)12] as a homogeneous catalyst in a reaction involving cyclohexene, methanol, and CO2 in the presence of an ionic liquid, 1-Butyl-3-methylimidazolium chloride ([BMIM]+Cl-). 1H NMR and ATR-FT-IR were utilized to characterize [BMIM]+Cl-. The reaction product was characterised utilizing GC-MS. Upon seeing that Ru3(CO)12 changes color from orange to black when exposed to heat, an investigation was undertaken on the kind of transformations that the catalyst undergoes. This investigation was carried out with the hopes of finding the structures that could be resulting from Ru3(CO)12 during the reaction and their significance to it. The orange and black Ru complexes were characterized utilizing DSC, TGA, ATR-FT-IR and PXRD. , Thesis (MSc) -- Faculty of Science, Chemistry, 2024
- Full Text:
- Date Issued: 2024-10-11
Cocrystals, salts and eutectics of anti-tuberculosis medicines
- Authors: Matlapeng, Tsebang Alice
- Date: 2024-10-11
- Subjects: Uncatalogued
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/464521 , vital:76518
- Description: Tuberculosis remains as a prominent cause of death worldwide. This infectious disease is treated with first and second line drugs. However, challenges of multi drug resistant tuberculosis and adverse side effects such as depletion of essential B group vitamins in the body by first line drugs, as well as poor physicochemical properties of second line drugs persist. Cocrystallisation of anti-tubercular drugs with various coformers has therefore been used as an alternative method to improve the physicochemical properties of active pharmaceutical ingredients (API) while maintaining their efficacy. The main objective of this study was to carry out cocrystal screening of anti-tubercular API and vitamin B coformers to make drug-drug or drug-vitamin multicomponent complexes. Preparation of the multicomponent complexes was carried out by mechanochemical grinding (neat grinding (NG), liquid assisted grinding (LAG) and slow evaporation. All complexes were characterised using Fourier-transform infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and crystal structures were elucidated using single-crystal X-ray diffraction (SCXRD). The cocrystal screening resulted in the formation of various solid forms, which included cocrystals, salts and eutectic products. Two cocrystals of 4-aminosalicylic acid (PAS) were isolated and characterised. The cocrystal of PAS with isoniazid (INH) demonstrated similar characteristics for both the bulk crystalline material and milled materials. The cocrystal of PAS and pyrazinamide (PYR) prepared using mechanochemical synthesis was met with challenges, while difficulties were also encountered in obtaining suitable crystals for SCXRD analysis. The ground and recrystallised samples of the PAS and pyrazinecarboxylic acid (PCBA) showed distinct differences in their thermal behaviour, with SCXRD revealing the decomposition product phenolammonium-pyrazinecarboxylate salt ‘sans’ the CO2 moiety. Salt formation involving pyridoxine (PN) yielded a salt hydrate with PAS (PN-PAS) and an anhydrous salt with PCBA (PN-PCBA). Both salts exhibited very complex packing arrangements with equally complex thermal behaviour depending on the solvent used during preparation, and the method of preparation. Three eutectic systems involving INH with PYR, PN and pyridoxine hydrochloride (PNꞏHCl) were identified, and their phase diagrams were constructed from DSC data. The eutectic compositions obtained were 1:1 for INH:PYR, 1:1 for INH:PN and 6:4 for INH:PNꞏHCl. Finally, a total of eight multicomponent complexes were prepared using selected API and vitamin B6 components. The results presented here provide motivation for further investigation and evaluation of the pharmacochemical properties of these API. , Thesis (MSc) -- Faculty of Science, Chemistry, 2024
- Full Text:
- Date Issued: 2024-10-11
- Authors: Matlapeng, Tsebang Alice
- Date: 2024-10-11
- Subjects: Uncatalogued
- Language: English
- Type: Academic theses , Master's theses , text
- Identifier: http://hdl.handle.net/10962/464521 , vital:76518
- Description: Tuberculosis remains as a prominent cause of death worldwide. This infectious disease is treated with first and second line drugs. However, challenges of multi drug resistant tuberculosis and adverse side effects such as depletion of essential B group vitamins in the body by first line drugs, as well as poor physicochemical properties of second line drugs persist. Cocrystallisation of anti-tubercular drugs with various coformers has therefore been used as an alternative method to improve the physicochemical properties of active pharmaceutical ingredients (API) while maintaining their efficacy. The main objective of this study was to carry out cocrystal screening of anti-tubercular API and vitamin B coformers to make drug-drug or drug-vitamin multicomponent complexes. Preparation of the multicomponent complexes was carried out by mechanochemical grinding (neat grinding (NG), liquid assisted grinding (LAG) and slow evaporation. All complexes were characterised using Fourier-transform infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and crystal structures were elucidated using single-crystal X-ray diffraction (SCXRD). The cocrystal screening resulted in the formation of various solid forms, which included cocrystals, salts and eutectic products. Two cocrystals of 4-aminosalicylic acid (PAS) were isolated and characterised. The cocrystal of PAS with isoniazid (INH) demonstrated similar characteristics for both the bulk crystalline material and milled materials. The cocrystal of PAS and pyrazinamide (PYR) prepared using mechanochemical synthesis was met with challenges, while difficulties were also encountered in obtaining suitable crystals for SCXRD analysis. The ground and recrystallised samples of the PAS and pyrazinecarboxylic acid (PCBA) showed distinct differences in their thermal behaviour, with SCXRD revealing the decomposition product phenolammonium-pyrazinecarboxylate salt ‘sans’ the CO2 moiety. Salt formation involving pyridoxine (PN) yielded a salt hydrate with PAS (PN-PAS) and an anhydrous salt with PCBA (PN-PCBA). Both salts exhibited very complex packing arrangements with equally complex thermal behaviour depending on the solvent used during preparation, and the method of preparation. Three eutectic systems involving INH with PYR, PN and pyridoxine hydrochloride (PNꞏHCl) were identified, and their phase diagrams were constructed from DSC data. The eutectic compositions obtained were 1:1 for INH:PYR, 1:1 for INH:PN and 6:4 for INH:PNꞏHCl. Finally, a total of eight multicomponent complexes were prepared using selected API and vitamin B6 components. The results presented here provide motivation for further investigation and evaluation of the pharmacochemical properties of these API. , Thesis (MSc) -- Faculty of Science, Chemistry, 2024
- Full Text:
- Date Issued: 2024-10-11
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