An investigation of the long term chemical stability and physical performance of PMD-citronellal acetal compared with dibutyl phthalate and BIS(2-ethylhexyl) terephthalate as plasticisers in selected cosmetic formulations
- Authors: Marx, Amor
- Date: 2019
- Subjects: Plastics -- Additives , Chemistry, Technical , Cosmetics
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: http://hdl.handle.net/10948/42574 , vital:36669
- Description: Plasticisers are used by cosmetic manufacturers to improve the film forming abilities of a product and increase flexibility of the film formed on the skin or hair surface, as is desired, for example, in nail lacquers and lip coats. In recent years authorities have banned several plasticisers in cosmetic products (mainly phthalates) since these substances may pose a wide range of health risks and can be harmful to the environment. It is, therefore, necessary to find alternative, safe plasticisers, preferably of natural origin e.g. bio-plasticisers which can replace the toxic phthalates and still impart the same desirable properties to the cosmetic products in which they are used. In this study, the novel bio-plasticiser para-menthane-3,8-diol-citronellal acetal (PMD-citronellal acetal) was selected to compare its stability properties and plasticising behaviour with well-known non-phthalate bis(2-ethylhexyl) terephthalate (DEHT) and the problematic dibutyl phthalate (DBP). The objectives were to determine if the novel bio-plasticiser PMD-citronellal acetal plasticising properties and chemical stability are similar or better than DEHT and DBP within two cosmetic formulations, viz. a nail lacquer and a lip coat formulation, after being incubated at elevated temperature (40 ˚C) over a three month period. The results showed that flexibility for all plasticised formulations remained stable at room temperature (21 ˚C) and elevated temperature (40 ˚C). Adhesion performance of DEHT and PMD-citronellal acetal nail lacquer formulations outperformed DBP nail lacquer formulations. Elevated temperature and storage time had no influence on the organoleptic properties of any plasticised formulation. PMD-citronellal acetal plasticised lip coat and nail lacquer formulations outperformed both DEHT and DBP nail formulations with regard to hardness. Fourier Transform Infrared Spectrometry (FTIR) studies revealed that neat DPB, DEHT and Acetal were chemically stable at room temperature and elevated temperature over a three month incubation period. Furthermore, the three plasticised nail lacquer and lip coat formulations remained chemical stable over the three month incubation period at elevated temperature. Chemical stability of the nail lacquer formulations was further evaluated by means of leaching tests using Solid Phase Extraction [1] and Ultra-Performance Liquid Chromatography (UPLC) at two temperatures (31 and 50 °C) and three time intervals (24, 48 and 72 hours). No leaching out of the nail lacquer formulation for Acetal and DEHT could be detected. It was observed that trace amounts of DBP leached from the nail lacquer formulation at 50 °C. DBP leaching decreased over time and was found to be statistically significant over the studied period. It can be concluded that PMD-citronellal acetal can be selected as bio-plasticiser which exhibits similar properties to DEHT based on the performance stability and non-leaching criteria, and can be used as an alternative plasticiser to the toxic DBP in cosmetic formulations.
- Full Text:
- Date Issued: 2019
- Authors: Marx, Amor
- Date: 2019
- Subjects: Plastics -- Additives , Chemistry, Technical , Cosmetics
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: http://hdl.handle.net/10948/42574 , vital:36669
- Description: Plasticisers are used by cosmetic manufacturers to improve the film forming abilities of a product and increase flexibility of the film formed on the skin or hair surface, as is desired, for example, in nail lacquers and lip coats. In recent years authorities have banned several plasticisers in cosmetic products (mainly phthalates) since these substances may pose a wide range of health risks and can be harmful to the environment. It is, therefore, necessary to find alternative, safe plasticisers, preferably of natural origin e.g. bio-plasticisers which can replace the toxic phthalates and still impart the same desirable properties to the cosmetic products in which they are used. In this study, the novel bio-plasticiser para-menthane-3,8-diol-citronellal acetal (PMD-citronellal acetal) was selected to compare its stability properties and plasticising behaviour with well-known non-phthalate bis(2-ethylhexyl) terephthalate (DEHT) and the problematic dibutyl phthalate (DBP). The objectives were to determine if the novel bio-plasticiser PMD-citronellal acetal plasticising properties and chemical stability are similar or better than DEHT and DBP within two cosmetic formulations, viz. a nail lacquer and a lip coat formulation, after being incubated at elevated temperature (40 ˚C) over a three month period. The results showed that flexibility for all plasticised formulations remained stable at room temperature (21 ˚C) and elevated temperature (40 ˚C). Adhesion performance of DEHT and PMD-citronellal acetal nail lacquer formulations outperformed DBP nail lacquer formulations. Elevated temperature and storage time had no influence on the organoleptic properties of any plasticised formulation. PMD-citronellal acetal plasticised lip coat and nail lacquer formulations outperformed both DEHT and DBP nail formulations with regard to hardness. Fourier Transform Infrared Spectrometry (FTIR) studies revealed that neat DPB, DEHT and Acetal were chemically stable at room temperature and elevated temperature over a three month incubation period. Furthermore, the three plasticised nail lacquer and lip coat formulations remained chemical stable over the three month incubation period at elevated temperature. Chemical stability of the nail lacquer formulations was further evaluated by means of leaching tests using Solid Phase Extraction [1] and Ultra-Performance Liquid Chromatography (UPLC) at two temperatures (31 and 50 °C) and three time intervals (24, 48 and 72 hours). No leaching out of the nail lacquer formulation for Acetal and DEHT could be detected. It was observed that trace amounts of DBP leached from the nail lacquer formulation at 50 °C. DBP leaching decreased over time and was found to be statistically significant over the studied period. It can be concluded that PMD-citronellal acetal can be selected as bio-plasticiser which exhibits similar properties to DEHT based on the performance stability and non-leaching criteria, and can be used as an alternative plasticiser to the toxic DBP in cosmetic formulations.
- Full Text:
- Date Issued: 2019
Agribusiness challenges to effectiveness of contract farming in commercialisation of small-scale vegetable farmers
- Authors: Khapayi, Musa
- Date: 2017
- Subjects: Farms, Small -- South Africa -- Eastern Cape , Agriculture -- Economic aspects -- South Africa -- Eastern Cape , Agricultural industries -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: http://hdl.handle.net/10948/13981 , vital:27363
- Description: The spread of contract farming in South Africa in recent years has provoked an ideological debate in literature. Linking small-scale vegetable farmers with lucrative agricultural markets through agribusiness value chains is seen as one of the foremost emerging agricultural practices to develop the subsistence farming sector into a mainstream economic sector – thereby revitalising the rural economy and alleviating poverty levels in the developing rural areas of South Africa. However, the challenges agribusiness and small-scale farmers experience in contract farming engagement and the prospects for enhancing the inclusion of small-scale farmers into modern value chains remain open to debate – two decades after transition to democracy. Yet the factors and mechanisms influencing the effective application of contract farming in the transition to commercial farming by small-scale farmers have not been thoroughly explored in South African research. Despite the efforts and the substantial investments made and the various policies and initiatives instigated to fast-track the linkages of small-scale farmers into high-value markets, the success stories of previously disadvantaged farmers operating in commercial agri-food chains are rare. Given the millions of small-scale farmers in former homelands alone, the negligible number of small-scale farmers successfully operating in commercial agri-food chains shows that the objectives to enable small-scale farmers to improve their livelihoods through participation in commercial agri-food chains have not yet been met. The broad objectives of the study were therefore to investigate the agribusiness challenges inherent in contract farming and the conditions and incentives required by agribusiness firms to engage small-scale vegetable farmers in contract farming programmes. Furthermore, the study examined the role played by the South African government to reduce the high transaction costs incurred by agribusinesses when engaging small-scale farmers in contractual arrangements. The Amathole and Sarah Baartman (formerly Cacadu) district municipalities in the Eastern Cape Province of South Africa were chosen as the composite survey area for this study. A predominantly qualitative research approach was applied to gather data on the phenomena under study. The following methodologies and research instruments and tools were selected. Firstly – as the secondary component of the research – a systematic review of literature to date was conducted to guide the empirical research and primary methodology. Secondly, the empirical component of the study comprised a questionnaire survey, unstructured interviews and focus group discussions. The questionnaire survey was used to collect data from the agribusiness firms in the area surveyed concerning the following aspects: the significant determinants of contract farming, the incentives required by the agribusiness firms to engage small-scale vegetable farmers in their contract farming programmes and the challenges faced by agribusiness firms in their interaction with small-scale farmers in contractual arrangements. Unstructured interviews were used to gather data from officials at each of the three levels of government – the Department of Rural Development and Land Reform nationally, Department of Agriculture and Land Reform provincially and (at local government level) two district municipalities – on the role played by government to reduce the high transaction costs incurred by agri-firms when procuring agricultural raw materials from small-scale vegetable farmers. Focus group discussions were conducted with small-scale farmers regarding their perspective on working with agribusiness firms and to establish the distinguishing characteristics of small-scale farmers in the area surveyed. Relevant policy documents collected from two of the three representative groups of the study population, i.e. agribusiness personnel and government officials, provided the essential context. The study revealed a limited number of contract farming business linkages between small-scale vegetable farmers and agribusiness firms in the survey area. Those that do exist are problematic to both the agribusiness firms and the small-scale farmers. It emerged that the contract farming environment in the area surveyed is highly polarised and characterised by a fundamental conflict of interest between agribusiness and farmer. Among the divergent key factors inhibiting contract farming engagement were a lack in terms of quality seeds, trust, entrepreneurial skills and formal contract agreements. Asset endowment (both land and non-land assets) was found to be significant pre-selection determinants in the farmer’s capacity to be contracted. Access to innovative technology, as well as government incentives such as production inputs, were found to be critical to agribusiness firms to engage smallscale farmers in their contract farming programmes. Government assistance in terms of high transaction costs to agribusiness firms working with large groups of small-scale farmers was found to be essential but inadequate under current policy. This impacts directly on the effectiveness and promotion of contract farming. Furthermore, the current results corroborate the findings of numerous South African studies in the vast body of worldwide research. Firstly, lack of land and non-land assets continue to be major impediments to the direct participa-tion of small-scale farmers in contract farming programmes and, secondly, the transaction and market information costs incurred by agribusiness prevent the participation of less endowed farmers in contract farming programmes. Conducted within the interpretivist paradigm, the explorative research identified wide-ranging challenges in the relationship between agri-business and small-scale farmers which directly impact the effective-ness of contract farming as a development and agrarian reform strategy. Despite their problematic relationship, however, agribusiness and small-scale contract farmers were in agreement that the government needs to expand its support for agri-firms to incentivise greater numbers of small-scale farmers having the opportunity to achieve commercial status through contract farming. The study therefore recommends a collaborative partnership between private firms and government, with state support through revised policies and development programmes. These amendments are crucial to enhancing the engagement of small-scale vegetable farmers in lucrative agri-food chains.
- Full Text:
- Date Issued: 2017
- Authors: Khapayi, Musa
- Date: 2017
- Subjects: Farms, Small -- South Africa -- Eastern Cape , Agriculture -- Economic aspects -- South Africa -- Eastern Cape , Agricultural industries -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: http://hdl.handle.net/10948/13981 , vital:27363
- Description: The spread of contract farming in South Africa in recent years has provoked an ideological debate in literature. Linking small-scale vegetable farmers with lucrative agricultural markets through agribusiness value chains is seen as one of the foremost emerging agricultural practices to develop the subsistence farming sector into a mainstream economic sector – thereby revitalising the rural economy and alleviating poverty levels in the developing rural areas of South Africa. However, the challenges agribusiness and small-scale farmers experience in contract farming engagement and the prospects for enhancing the inclusion of small-scale farmers into modern value chains remain open to debate – two decades after transition to democracy. Yet the factors and mechanisms influencing the effective application of contract farming in the transition to commercial farming by small-scale farmers have not been thoroughly explored in South African research. Despite the efforts and the substantial investments made and the various policies and initiatives instigated to fast-track the linkages of small-scale farmers into high-value markets, the success stories of previously disadvantaged farmers operating in commercial agri-food chains are rare. Given the millions of small-scale farmers in former homelands alone, the negligible number of small-scale farmers successfully operating in commercial agri-food chains shows that the objectives to enable small-scale farmers to improve their livelihoods through participation in commercial agri-food chains have not yet been met. The broad objectives of the study were therefore to investigate the agribusiness challenges inherent in contract farming and the conditions and incentives required by agribusiness firms to engage small-scale vegetable farmers in contract farming programmes. Furthermore, the study examined the role played by the South African government to reduce the high transaction costs incurred by agribusinesses when engaging small-scale farmers in contractual arrangements. The Amathole and Sarah Baartman (formerly Cacadu) district municipalities in the Eastern Cape Province of South Africa were chosen as the composite survey area for this study. A predominantly qualitative research approach was applied to gather data on the phenomena under study. The following methodologies and research instruments and tools were selected. Firstly – as the secondary component of the research – a systematic review of literature to date was conducted to guide the empirical research and primary methodology. Secondly, the empirical component of the study comprised a questionnaire survey, unstructured interviews and focus group discussions. The questionnaire survey was used to collect data from the agribusiness firms in the area surveyed concerning the following aspects: the significant determinants of contract farming, the incentives required by the agribusiness firms to engage small-scale vegetable farmers in their contract farming programmes and the challenges faced by agribusiness firms in their interaction with small-scale farmers in contractual arrangements. Unstructured interviews were used to gather data from officials at each of the three levels of government – the Department of Rural Development and Land Reform nationally, Department of Agriculture and Land Reform provincially and (at local government level) two district municipalities – on the role played by government to reduce the high transaction costs incurred by agri-firms when procuring agricultural raw materials from small-scale vegetable farmers. Focus group discussions were conducted with small-scale farmers regarding their perspective on working with agribusiness firms and to establish the distinguishing characteristics of small-scale farmers in the area surveyed. Relevant policy documents collected from two of the three representative groups of the study population, i.e. agribusiness personnel and government officials, provided the essential context. The study revealed a limited number of contract farming business linkages between small-scale vegetable farmers and agribusiness firms in the survey area. Those that do exist are problematic to both the agribusiness firms and the small-scale farmers. It emerged that the contract farming environment in the area surveyed is highly polarised and characterised by a fundamental conflict of interest between agribusiness and farmer. Among the divergent key factors inhibiting contract farming engagement were a lack in terms of quality seeds, trust, entrepreneurial skills and formal contract agreements. Asset endowment (both land and non-land assets) was found to be significant pre-selection determinants in the farmer’s capacity to be contracted. Access to innovative technology, as well as government incentives such as production inputs, were found to be critical to agribusiness firms to engage smallscale farmers in their contract farming programmes. Government assistance in terms of high transaction costs to agribusiness firms working with large groups of small-scale farmers was found to be essential but inadequate under current policy. This impacts directly on the effectiveness and promotion of contract farming. Furthermore, the current results corroborate the findings of numerous South African studies in the vast body of worldwide research. Firstly, lack of land and non-land assets continue to be major impediments to the direct participa-tion of small-scale farmers in contract farming programmes and, secondly, the transaction and market information costs incurred by agribusiness prevent the participation of less endowed farmers in contract farming programmes. Conducted within the interpretivist paradigm, the explorative research identified wide-ranging challenges in the relationship between agri-business and small-scale farmers which directly impact the effective-ness of contract farming as a development and agrarian reform strategy. Despite their problematic relationship, however, agribusiness and small-scale contract farmers were in agreement that the government needs to expand its support for agri-firms to incentivise greater numbers of small-scale farmers having the opportunity to achieve commercial status through contract farming. The study therefore recommends a collaborative partnership between private firms and government, with state support through revised policies and development programmes. These amendments are crucial to enhancing the engagement of small-scale vegetable farmers in lucrative agri-food chains.
- Full Text:
- Date Issued: 2017
Continuous flow synthesis of silicon compounds as feedstock for solar-grade silicon production
- Authors: Chigondo, Fidelis
- Date: 2016
- Subjects: Silicon -- Synthesis , Homogeneous catalysis
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: http://hdl.handle.net/10948/4529 , vital:20613
- Description: This thesis describes the key steps in the production of high purity (solar-grade) silicon from metallurgical-grade silicon for use in the production of photovoltaic cells as alternative renewable, environmentally benign and cheap energy source. The initial part of the project involves the development and optimization of a small chemical production platform system capable of producing alkoxysilanes from metallurgical-grade silicon as green precursors to solar-grade silicon production. Specifically, the main aim of the study was to synthesize trialkoxysilanes in continuous flow mode, although the synthesis on monosilane was also done in batch mode. The alkoxylation reaction was carried out in a traditional slurry phase batch reactor, packed bed flow tubular reactor and also attempted in a continuous flow falling film tubular reactor. The effect of key parameters which affect the silicon conversion and selectivity for the desired trialkoxysilane were investigated and optimized using ethanol as a reagent model. The synthesis was then extended to the other alcohols namely methanol, n-propanol and n-butanol. Copper catalysts which were tested in the alkoxylation reaction included: CuCl, Cu(OH)2, CuO and CuSO4. CuCl and Cu(OH)2 showed comparable activity in the batch mode but the former was more efficient in the packed bed flow tubular reactor. Cu(OH)2 could be used as a non-halide catalyst but its activity is limited to short reaction cycles (<10 h). The uncatalysed reaction resulted in negligible reaction rates in both types of reactors. High temperature catalyst pre-heating (>500 oC) resulted in a lower rate of reaction and selectivity than when slightly lower temperatures are used (<350 oC) in both reactors, although much difference was noticed in the packed bed flow tubular reactor. Synthesis in the batch reactor needed longer silicon-catalyst activation time, higher pre-heating temperature and higher catalyst amounts as compare to the packed bed flow tubular reactor. Reaction temperature and alcohol flow rate influenced the reaction in both methods. The optimum reaction temperature range and alcohol flow rate was comparable in both reactors (230 to 240 oC) and 0.1mL/min respectively. The effect of alcohol R-group (C1 to C4) on the reaction revealed that conversion and selectivity generally decrease with an increase in carbon chain length in both methods. Ethanol showed highest selectivity (>95% in batch and >97% in flow) and conversion (about 88% in batch and about 64% in flow) as compared to all other alcohols studied showing that it could be the most efficient alkoxylation alcohol for this reaction. Overally, the packed bed flow tubular reactor resulted in higher selectivity to trialkoxysilanes than the batch system. Performing the reaction under pressure resulted in increased conversion but selectivity to the desire trialkoxysilane diminished. Synthesis in a continuous flow falling film tubular reactor was not successful as it resulted in very poor conversion and selectivity. Monosilane was successfully synthesized from the disproportionation of triethoxysilane using homogeneous and heterogeneous catalysts in batch mode. The results obtained from homogeneous catalysis showed that the reaction can be conducted at room temperature. The heterogeneous catalysis method resulted in slow conversion at room temperature but mild heating up to 55 oC greatly improved the reaction. Conducting the reaction under neat conditions produced comparable results to reactions which were carried out using solvents. The disproportionation reaction was best described by the first order kinetic model. The results obtained in this research indicate that the packed bed flow tubular reactor can be utilized with future modifications for continuous flow synthesis of alkoxysilanes as feedstock for the solar-grade silicon production.
- Full Text:
- Date Issued: 2016
- Authors: Chigondo, Fidelis
- Date: 2016
- Subjects: Silicon -- Synthesis , Homogeneous catalysis
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: http://hdl.handle.net/10948/4529 , vital:20613
- Description: This thesis describes the key steps in the production of high purity (solar-grade) silicon from metallurgical-grade silicon for use in the production of photovoltaic cells as alternative renewable, environmentally benign and cheap energy source. The initial part of the project involves the development and optimization of a small chemical production platform system capable of producing alkoxysilanes from metallurgical-grade silicon as green precursors to solar-grade silicon production. Specifically, the main aim of the study was to synthesize trialkoxysilanes in continuous flow mode, although the synthesis on monosilane was also done in batch mode. The alkoxylation reaction was carried out in a traditional slurry phase batch reactor, packed bed flow tubular reactor and also attempted in a continuous flow falling film tubular reactor. The effect of key parameters which affect the silicon conversion and selectivity for the desired trialkoxysilane were investigated and optimized using ethanol as a reagent model. The synthesis was then extended to the other alcohols namely methanol, n-propanol and n-butanol. Copper catalysts which were tested in the alkoxylation reaction included: CuCl, Cu(OH)2, CuO and CuSO4. CuCl and Cu(OH)2 showed comparable activity in the batch mode but the former was more efficient in the packed bed flow tubular reactor. Cu(OH)2 could be used as a non-halide catalyst but its activity is limited to short reaction cycles (<10 h). The uncatalysed reaction resulted in negligible reaction rates in both types of reactors. High temperature catalyst pre-heating (>500 oC) resulted in a lower rate of reaction and selectivity than when slightly lower temperatures are used (<350 oC) in both reactors, although much difference was noticed in the packed bed flow tubular reactor. Synthesis in the batch reactor needed longer silicon-catalyst activation time, higher pre-heating temperature and higher catalyst amounts as compare to the packed bed flow tubular reactor. Reaction temperature and alcohol flow rate influenced the reaction in both methods. The optimum reaction temperature range and alcohol flow rate was comparable in both reactors (230 to 240 oC) and 0.1mL/min respectively. The effect of alcohol R-group (C1 to C4) on the reaction revealed that conversion and selectivity generally decrease with an increase in carbon chain length in both methods. Ethanol showed highest selectivity (>95% in batch and >97% in flow) and conversion (about 88% in batch and about 64% in flow) as compared to all other alcohols studied showing that it could be the most efficient alkoxylation alcohol for this reaction. Overally, the packed bed flow tubular reactor resulted in higher selectivity to trialkoxysilanes than the batch system. Performing the reaction under pressure resulted in increased conversion but selectivity to the desire trialkoxysilane diminished. Synthesis in a continuous flow falling film tubular reactor was not successful as it resulted in very poor conversion and selectivity. Monosilane was successfully synthesized from the disproportionation of triethoxysilane using homogeneous and heterogeneous catalysts in batch mode. The results obtained from homogeneous catalysis showed that the reaction can be conducted at room temperature. The heterogeneous catalysis method resulted in slow conversion at room temperature but mild heating up to 55 oC greatly improved the reaction. Conducting the reaction under neat conditions produced comparable results to reactions which were carried out using solvents. The disproportionation reaction was best described by the first order kinetic model. The results obtained in this research indicate that the packed bed flow tubular reactor can be utilized with future modifications for continuous flow synthesis of alkoxysilanes as feedstock for the solar-grade silicon production.
- Full Text:
- Date Issued: 2016
The development and evaluation of a new manufacturing process for β-sitosterol-D glucoside
- Mtyopo, Mthetheleli Bethwell
- Authors: Mtyopo, Mthetheleli Bethwell
- Date: 2016
- Subjects: Pharmaceutical chemistry Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: http://hdl.handle.net/10948/45920 , vital:39320
- Description: The existing production sequence of β-sitosterol-D-glucoside, a glucoside used in an “over-the-counter” (OTC) preparation under the brand name of Moducare® comprises of three process steps with an overall yield of less than 20%. The low yield is partly due to the instability of intermediates at reaction temperatures > 0oC, and partly due to the thermodynamic equilibrium between two stereoisomers. An economically alternative process was developed, evaluated and scaled-up in a 2l reactor. The project was initiated with a specific limitation in terms of the starting material that comprised a mixture of plant sterols, which necessitated a study of the isolation and purification of the desired product from a rather complex reaction mixture. The use of silver as halide acceptor for the Koenigs-Knorr synthesis did not give statistically significant different results from the same approach but using cadmium as halide acceptor instead. However, using the direct O-glucosylation approach not only gave statistically significant higher results, but also resulted in a much more convenient procedure. Under optimum conditions, a yield of approximately 83% (isolated) of 2,3,4,6- tetra-О-acetyl-β-sitosterol-D-glucoside could be achieved, which was substantially higher than that achieved with the traditional Koenigs-Knorr methodology and above reported yields in the literature (60-80%) for direct glycosylation. Separation of 2,3,4,6-tetra-О-acetyl-β-sitosterol-D-glucoside (BSSGT) from a reaction mixture that contains 2,3,4,6-tetra-О-acetyl-campesterol-D-glucoside (CSGT), 2,3,4,6-tetra-О-acetyl campestanol-glucoside (CSSGT), and 2,3,4,6-tetra-О-acetyl-sitostanol-Dglucoside (SSGT) was investigated using column chromatography. When using silica gel particles, very good separation efficiency and product recovery could be achieved using hexane/ethyl hexane as eluent. The isolated 2,3,4,6-tetra-О-acetyl-β-sitosterol-Dglucoside was easily hydrolysed to β-sitosterol-D-glucoside in high yields (79%) using methanolic KOH. The process for the production of β-sitosterol-D-glucoside was scaled-up from the laboratory bench scale (250 cm3) to a laboratory scale of 2 l using the direct Oglycosylation method. The overall yields of the scaled reaction for β-sitosterol-D-glucoside was slightly above the literature reported values (59%, 8/92) for the KnoenigsKnorr synthesis and compares well above (62%, 0/100) the current production process (less than 20% yields). When using catalogue prices, the material costs (without recycling) for the direct Oglucosylation route is approximately 57% less for the synthesis of 1kg of β-sitosterol-Dglucoside compared to the Koenigs-Knorr route. Given further savings for recycling, the direct O-glucosylation route provides an attractive alternative route for the synthesis ofthe target compound.
- Full Text:
- Date Issued: 2016
- Authors: Mtyopo, Mthetheleli Bethwell
- Date: 2016
- Subjects: Pharmaceutical chemistry Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: http://hdl.handle.net/10948/45920 , vital:39320
- Description: The existing production sequence of β-sitosterol-D-glucoside, a glucoside used in an “over-the-counter” (OTC) preparation under the brand name of Moducare® comprises of three process steps with an overall yield of less than 20%. The low yield is partly due to the instability of intermediates at reaction temperatures > 0oC, and partly due to the thermodynamic equilibrium between two stereoisomers. An economically alternative process was developed, evaluated and scaled-up in a 2l reactor. The project was initiated with a specific limitation in terms of the starting material that comprised a mixture of plant sterols, which necessitated a study of the isolation and purification of the desired product from a rather complex reaction mixture. The use of silver as halide acceptor for the Koenigs-Knorr synthesis did not give statistically significant different results from the same approach but using cadmium as halide acceptor instead. However, using the direct O-glucosylation approach not only gave statistically significant higher results, but also resulted in a much more convenient procedure. Under optimum conditions, a yield of approximately 83% (isolated) of 2,3,4,6- tetra-О-acetyl-β-sitosterol-D-glucoside could be achieved, which was substantially higher than that achieved with the traditional Koenigs-Knorr methodology and above reported yields in the literature (60-80%) for direct glycosylation. Separation of 2,3,4,6-tetra-О-acetyl-β-sitosterol-D-glucoside (BSSGT) from a reaction mixture that contains 2,3,4,6-tetra-О-acetyl-campesterol-D-glucoside (CSGT), 2,3,4,6-tetra-О-acetyl campestanol-glucoside (CSSGT), and 2,3,4,6-tetra-О-acetyl-sitostanol-Dglucoside (SSGT) was investigated using column chromatography. When using silica gel particles, very good separation efficiency and product recovery could be achieved using hexane/ethyl hexane as eluent. The isolated 2,3,4,6-tetra-О-acetyl-β-sitosterol-Dglucoside was easily hydrolysed to β-sitosterol-D-glucoside in high yields (79%) using methanolic KOH. The process for the production of β-sitosterol-D-glucoside was scaled-up from the laboratory bench scale (250 cm3) to a laboratory scale of 2 l using the direct Oglycosylation method. The overall yields of the scaled reaction for β-sitosterol-D-glucoside was slightly above the literature reported values (59%, 8/92) for the KnoenigsKnorr synthesis and compares well above (62%, 0/100) the current production process (less than 20% yields). When using catalogue prices, the material costs (without recycling) for the direct Oglucosylation route is approximately 57% less for the synthesis of 1kg of β-sitosterol-Dglucoside compared to the Koenigs-Knorr route. Given further savings for recycling, the direct O-glucosylation route provides an attractive alternative route for the synthesis ofthe target compound.
- Full Text:
- Date Issued: 2016
Causal determinants of the public's attitudes towards hunting as a basis for strategies to improve the social legitimacy of hunting
- Coetzer, Wentzel Christoffel
- Authors: Coetzer, Wentzel Christoffel
- Date: 2014
- Subjects: Hunting -- South Africa , Wildlife management -- South Africa , Wildlife conservation -- South Africa
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10759 , http://hdl.handle.net/10948/d1021164
- Description: It is widely acknowledged that the organised wildlife and hunting industry in South Africa contributes significantly to the country’s economy, as well as to the effective management and conservation of wildlife on privately owned land. Despite this, hunting has come under increasing attack by anti-hunting proponents who wish to bring a ban on hunting. A number of broad shifts across society at large and lobbying against hunting by anti-hunting proponents have given rise to legitimate concerns regarding the social acceptability of hunting. To maintain the social legitimacy of hunting, it is imperative to put strategies in place to actively broaden the base of public acceptance of hunting. Towards this aim, this study is an empirical investigation of the causal determinants of the public’s attitudes towards hunting and of the implications it holds for improving the social legitimacy of hunting. The study commenced by building a sound theoretical foundation from the available literature on the measurement of attitudes, the structure and formation of attitudes, the instrumental and experiential aspects of attitudes, attitudinal ambivalence, the psychology of strong attitudes, as well as the phenomenon of cognitive dissonance. Thereafter, the study turned to identify an adequate and empirically valid research approach for investigating attitudes and its causal determinants. A popular attitude theory in social psychology, namely the theory of reasoned action, was identified as a suitable conceptual framework for conducting this study. According to the reasoned action model, the salient behavioural beliefs people associate with a particular behaviour form the informational foundation (or cognitive foundation) on which their attitudes towards the behaviour are based. More specifically, the model suggests that peoples’ overall attitude towards a behaviour is a function of their perceived probability that a behaviour will produce certain outcomes (belief strength), as well as the degree to which they judge the perceived outcomes of the behaviour as positive or negative (outcome evaluation). The methodological design of the study’s empirical component was strictly based on the standard procedures prescribed by the theory of reasoned action. Two consecutive and methodologically interrelated surveys were conducted amongst members of the public to collect the study’s primary data. The main salient behavioural beliefs on which different attitudes towards hunting are based were identified and further investigated. The results were analysed from the perspective of the theory of reasoned action and a clear understanding of the causal determinants of different attitudes towards hunting were attained. Based on the findings of the study, a number of conclusions and recommendations were made that may guide the development of future strategies to improve the social legitimacy of hunting. Amongst other things, it was suggested that public education programmes should be developed to address the public’s misconceptions of hunting; that public relation campaigns be undertaken to improve the public’s negative image of hunters; and that hunter education programmes be put in place to make hunters aware of the role they could play at community level to improve the social acceptability of hunting. Detailed guidelines regarding the contents of such education programmes and public relation campaigns were provided.
- Full Text:
- Date Issued: 2014
- Authors: Coetzer, Wentzel Christoffel
- Date: 2014
- Subjects: Hunting -- South Africa , Wildlife management -- South Africa , Wildlife conservation -- South Africa
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10759 , http://hdl.handle.net/10948/d1021164
- Description: It is widely acknowledged that the organised wildlife and hunting industry in South Africa contributes significantly to the country’s economy, as well as to the effective management and conservation of wildlife on privately owned land. Despite this, hunting has come under increasing attack by anti-hunting proponents who wish to bring a ban on hunting. A number of broad shifts across society at large and lobbying against hunting by anti-hunting proponents have given rise to legitimate concerns regarding the social acceptability of hunting. To maintain the social legitimacy of hunting, it is imperative to put strategies in place to actively broaden the base of public acceptance of hunting. Towards this aim, this study is an empirical investigation of the causal determinants of the public’s attitudes towards hunting and of the implications it holds for improving the social legitimacy of hunting. The study commenced by building a sound theoretical foundation from the available literature on the measurement of attitudes, the structure and formation of attitudes, the instrumental and experiential aspects of attitudes, attitudinal ambivalence, the psychology of strong attitudes, as well as the phenomenon of cognitive dissonance. Thereafter, the study turned to identify an adequate and empirically valid research approach for investigating attitudes and its causal determinants. A popular attitude theory in social psychology, namely the theory of reasoned action, was identified as a suitable conceptual framework for conducting this study. According to the reasoned action model, the salient behavioural beliefs people associate with a particular behaviour form the informational foundation (or cognitive foundation) on which their attitudes towards the behaviour are based. More specifically, the model suggests that peoples’ overall attitude towards a behaviour is a function of their perceived probability that a behaviour will produce certain outcomes (belief strength), as well as the degree to which they judge the perceived outcomes of the behaviour as positive or negative (outcome evaluation). The methodological design of the study’s empirical component was strictly based on the standard procedures prescribed by the theory of reasoned action. Two consecutive and methodologically interrelated surveys were conducted amongst members of the public to collect the study’s primary data. The main salient behavioural beliefs on which different attitudes towards hunting are based were identified and further investigated. The results were analysed from the perspective of the theory of reasoned action and a clear understanding of the causal determinants of different attitudes towards hunting were attained. Based on the findings of the study, a number of conclusions and recommendations were made that may guide the development of future strategies to improve the social legitimacy of hunting. Amongst other things, it was suggested that public education programmes should be developed to address the public’s misconceptions of hunting; that public relation campaigns be undertaken to improve the public’s negative image of hunters; and that hunter education programmes be put in place to make hunters aware of the role they could play at community level to improve the social acceptability of hunting. Detailed guidelines regarding the contents of such education programmes and public relation campaigns were provided.
- Full Text:
- Date Issued: 2014
A chemo-enzymatic process for the production of beta-thymidine, a key intermediate in antiretrovirol manufacture
- Gordon, Gregory Ernest Robert
- Authors: Gordon, Gregory Ernest Robert
- Date: 2010
- Subjects: HIV infections -- Treatment -- South Africa , HIV infections -- South Africa -- Prevention , Antiretroviral agents
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10423 , http://hdl.handle.net/10948/d1016217
- Description: The socio-economic impact of HIV/AIDS on South Africa has resulted in lower gross domestic product, loss of skills in key sectors such as education, and increased health-care costs in providing access to treatment. Currently active pharmaceutical ingredients (API’s) such as stavudine (d4T) and azidothymidine (AZT) are imported from India and China, while formulation is conducted locally. A strategy was initiated between CSIR Biosciences and LIFElab under the auspices of Arvir Technologies to investigate the feasibility of local antiretroviral manufacture (d4T and AZT) or the manufacture of a key intermediate such as β- thymidine (dT). Several advantages associated with successful implementation of this strategy include ensuring a local supply of API’s, thus reducing reliance on procurement from foreign sources and reducing the effect of foreign exchange rate fluctuations on providing cost effective access to treatment. A local supply source would also reduce the imports and thus aid the balance of payments deficit, and in addition to this, provide stimulus in the local pharmaceutical manufacturing industry (which has been in decline for several decades), resulting in increased skills and employment opportunities. This thesis describes the development of a superior chemo-enzymatic process for the production of β-thymidine (72 percent yield, prior to isolation), a key intermediate in the preparation of anti-retrovirals. Alternative processes based purely on chemical or bioprocess transformations to prepare either 5-methyluridine (5-MU) or dT suffer from several disadvantages: lengthy transformations due to protection/deprotection strategies, low selectivties and product yields (30 percent in the chemical process) and isolation of the product from dilute process streams requiring the use of large uneconomical reactors (bioprocesss). This contributes significantly to the cost of d4T and AZT manufacture. Our novel chemoenzymatic process comprises of a biocatalytic reaction for the production of 5-MU, with subsequent chemical transformation into dT (3 steps) negating and circumventing the limitations of the chemical or bioprocess routes. During the course of this project development, the β-thymidine selling price declined from 175 $/kg (2005) to 100 $/kg (2008). However, the process described in this work is still competitive based on the current β- thymidine selling price of 100 $/kg. The process economics show that with further optimization and increasing the isolated dT yield from 70 percent to 90 percent, the variable cost decreases from 136 $/kg to 110 $/kg. The increase in isolated yield is highly probable, based on solubility data of β-thymidine. The decrease in β-thymidine selling price and technological improvement in dT manufacture should translate into lower API manufacture costs and more cost effective access to treatment. Our novel biocatalytic process producing 5-MU uses a coupled enzyme system employing PNP, Purine Nucleoside Phosphorylase and PyNP, Pyrimidine Nucleoside Phosphorylase. The overall transglycosylation reaction may be decoupled into the phosphorolysis reaction (PNP) and synthesis reaction (PyNP). During the phosphorolysis reaction, guanosine is converted into guanine and ribose-1-phosphate (R-1-P) in the presence of PNP enzyme. The reaction intermediate R-1-P is then coupled to thymine in the presence of PyNP enzyme during the synthesis reaction, producing 5-MU. The process was scaled up from lab-scale to bench-scale (10 - 20 L) and demonstrated to be robust and reproducible. This is evident from the average guanosine conversion (94.7 percent ± 2.03) and 5-MU yield (88.2 percent ± 6.21) and mole balance (104 percent ± 7.61) which were obtained at bench-scale (3 replicates, 10 L). The reaction was carried out at reactor productivities of between 7 – 11 g.L-1.h-1. The integration of the biocatalytic process and chemical processes was successfully carried out, showing that 5-MU produced using our novel biocatalytic process behaved similarly to commercially available 5- MU (ex. Dayang Chemicals, China). A PCT patent application (Ref. No. P44422PC01) on this chemo-enzymatic process has been filed and currently public private partnerships are being explored through Arvir Technologies to evaluate and validate this technology at one ton scale.
- Full Text:
- Date Issued: 2010
- Authors: Gordon, Gregory Ernest Robert
- Date: 2010
- Subjects: HIV infections -- Treatment -- South Africa , HIV infections -- South Africa -- Prevention , Antiretroviral agents
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10423 , http://hdl.handle.net/10948/d1016217
- Description: The socio-economic impact of HIV/AIDS on South Africa has resulted in lower gross domestic product, loss of skills in key sectors such as education, and increased health-care costs in providing access to treatment. Currently active pharmaceutical ingredients (API’s) such as stavudine (d4T) and azidothymidine (AZT) are imported from India and China, while formulation is conducted locally. A strategy was initiated between CSIR Biosciences and LIFElab under the auspices of Arvir Technologies to investigate the feasibility of local antiretroviral manufacture (d4T and AZT) or the manufacture of a key intermediate such as β- thymidine (dT). Several advantages associated with successful implementation of this strategy include ensuring a local supply of API’s, thus reducing reliance on procurement from foreign sources and reducing the effect of foreign exchange rate fluctuations on providing cost effective access to treatment. A local supply source would also reduce the imports and thus aid the balance of payments deficit, and in addition to this, provide stimulus in the local pharmaceutical manufacturing industry (which has been in decline for several decades), resulting in increased skills and employment opportunities. This thesis describes the development of a superior chemo-enzymatic process for the production of β-thymidine (72 percent yield, prior to isolation), a key intermediate in the preparation of anti-retrovirals. Alternative processes based purely on chemical or bioprocess transformations to prepare either 5-methyluridine (5-MU) or dT suffer from several disadvantages: lengthy transformations due to protection/deprotection strategies, low selectivties and product yields (30 percent in the chemical process) and isolation of the product from dilute process streams requiring the use of large uneconomical reactors (bioprocesss). This contributes significantly to the cost of d4T and AZT manufacture. Our novel chemoenzymatic process comprises of a biocatalytic reaction for the production of 5-MU, with subsequent chemical transformation into dT (3 steps) negating and circumventing the limitations of the chemical or bioprocess routes. During the course of this project development, the β-thymidine selling price declined from 175 $/kg (2005) to 100 $/kg (2008). However, the process described in this work is still competitive based on the current β- thymidine selling price of 100 $/kg. The process economics show that with further optimization and increasing the isolated dT yield from 70 percent to 90 percent, the variable cost decreases from 136 $/kg to 110 $/kg. The increase in isolated yield is highly probable, based on solubility data of β-thymidine. The decrease in β-thymidine selling price and technological improvement in dT manufacture should translate into lower API manufacture costs and more cost effective access to treatment. Our novel biocatalytic process producing 5-MU uses a coupled enzyme system employing PNP, Purine Nucleoside Phosphorylase and PyNP, Pyrimidine Nucleoside Phosphorylase. The overall transglycosylation reaction may be decoupled into the phosphorolysis reaction (PNP) and synthesis reaction (PyNP). During the phosphorolysis reaction, guanosine is converted into guanine and ribose-1-phosphate (R-1-P) in the presence of PNP enzyme. The reaction intermediate R-1-P is then coupled to thymine in the presence of PyNP enzyme during the synthesis reaction, producing 5-MU. The process was scaled up from lab-scale to bench-scale (10 - 20 L) and demonstrated to be robust and reproducible. This is evident from the average guanosine conversion (94.7 percent ± 2.03) and 5-MU yield (88.2 percent ± 6.21) and mole balance (104 percent ± 7.61) which were obtained at bench-scale (3 replicates, 10 L). The reaction was carried out at reactor productivities of between 7 – 11 g.L-1.h-1. The integration of the biocatalytic process and chemical processes was successfully carried out, showing that 5-MU produced using our novel biocatalytic process behaved similarly to commercially available 5- MU (ex. Dayang Chemicals, China). A PCT patent application (Ref. No. P44422PC01) on this chemo-enzymatic process has been filed and currently public private partnerships are being explored through Arvir Technologies to evaluate and validate this technology at one ton scale.
- Full Text:
- Date Issued: 2010
Development of a process for the preparation of linalool from CIS-2-pinanol
- Authors: Buddoo, Subash Ramnarain
- Date: 2009
- Subjects: Odors , Perfumes -- History , Perfumes -- Formulae , Fermentation
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10425 , http://hdl.handle.net/10948/d1016219
- Description: Linalool is a key intermediate for the production of important fragrance chemicals such as geraniol, nerol, geranial, and neral. Linalool can be produced via a two-step process from α-pinene which is a major component of crude sulphated turpentine (CST) a foul-smelling, volatile waste product of the pulp and paper industry. The key step in this process is the pyrolysis step which involves the isomerisation of cis-2-pinanol to linalool and requires high temperatures (600-650°C) and is not very selective due to the decomposition of the product itself under these conditions. A client of the CSIR, Teubes Pty. Ltd., is a manufacturer of flavour and fragrance compounds for the local and international fragrance market and expressed an interest in producing linalool since the company would then gain access to other valuable fragrance chemicals via relatively simple processes. Earlier work conducted by AECI, R & D did not meet with much success since the selectivity to linalool was very poor and the process could hardly be deemed as scalable. The main objective of this project was therefore to develop a process for the selective isomerisation of cis-2-pinanol to linalool with minimum by-product formation and using process equipment that could be scaled to full-scale production. Since cis-2- pinanol could not be purchased in sufficient quantities for process development, a process had to be developed for the bench-scale preparation of kilogram quantities of cis-2-pinanol from α-pinene obtained from the client. Although this synthesis formed a minor part of this investigation, several process improvements and innovations were introduced to produce high quality cis-2-pinanol, in very good yields at kilogram scale. A major part of this investigation was the design and set up of a pyrolyis rig capable of operating at elevated temperatures (400 - 750°C) for the evaluation of various process parameters. Various vaporizer, reactor, and condensation systems were evaluated for their ability to cope with the demanding conditions on a consistent basis. The initial part of the investigation was a screening exercise to evaluate various process parameters as well as solvents, materials of construction, catalysts, etc. A comprehensive statistical design was also conducted to determine the critical process parameters and the model obtained was used to predict the optimum conditions required for the preparation of in-specification product on a consistent basis. These conditions were used in the preparation of a 1kg sample which was required by theclient for market evaluation purposes. The use of a novel microreactor system was also evaluated for the pinanol pyrolysis reaction. To our knowledge, this is the first time that a microreactor has been successfully used for this type of reaction in the Fragrance industry and a patent application is being filed by the CSIR. The kinetics of the reaction in both the tubular reactor system and the microreactor system was investigated. Computer modelling studies on both the systems were also conducted. The raw material cost to produce a kilogram of linalool is $1.40. There is a significant margin of 60.8 percent between the raw material cost of linalool and the current selling price ($3.57/kg). This clearly indicates that the project is potentially feasible from an economic point of view and we can now proceed with confidence to the next stage which is the engineering design, building and commissioning of the large scale pyrolysis rig. The rest of the process steps will be conducted on existing equipment currently present at the CSIR’s large scale facility (Imbiza in Isando, Gauteng).
- Full Text:
- Date Issued: 2009
- Authors: Buddoo, Subash Ramnarain
- Date: 2009
- Subjects: Odors , Perfumes -- History , Perfumes -- Formulae , Fermentation
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10425 , http://hdl.handle.net/10948/d1016219
- Description: Linalool is a key intermediate for the production of important fragrance chemicals such as geraniol, nerol, geranial, and neral. Linalool can be produced via a two-step process from α-pinene which is a major component of crude sulphated turpentine (CST) a foul-smelling, volatile waste product of the pulp and paper industry. The key step in this process is the pyrolysis step which involves the isomerisation of cis-2-pinanol to linalool and requires high temperatures (600-650°C) and is not very selective due to the decomposition of the product itself under these conditions. A client of the CSIR, Teubes Pty. Ltd., is a manufacturer of flavour and fragrance compounds for the local and international fragrance market and expressed an interest in producing linalool since the company would then gain access to other valuable fragrance chemicals via relatively simple processes. Earlier work conducted by AECI, R & D did not meet with much success since the selectivity to linalool was very poor and the process could hardly be deemed as scalable. The main objective of this project was therefore to develop a process for the selective isomerisation of cis-2-pinanol to linalool with minimum by-product formation and using process equipment that could be scaled to full-scale production. Since cis-2- pinanol could not be purchased in sufficient quantities for process development, a process had to be developed for the bench-scale preparation of kilogram quantities of cis-2-pinanol from α-pinene obtained from the client. Although this synthesis formed a minor part of this investigation, several process improvements and innovations were introduced to produce high quality cis-2-pinanol, in very good yields at kilogram scale. A major part of this investigation was the design and set up of a pyrolyis rig capable of operating at elevated temperatures (400 - 750°C) for the evaluation of various process parameters. Various vaporizer, reactor, and condensation systems were evaluated for their ability to cope with the demanding conditions on a consistent basis. The initial part of the investigation was a screening exercise to evaluate various process parameters as well as solvents, materials of construction, catalysts, etc. A comprehensive statistical design was also conducted to determine the critical process parameters and the model obtained was used to predict the optimum conditions required for the preparation of in-specification product on a consistent basis. These conditions were used in the preparation of a 1kg sample which was required by theclient for market evaluation purposes. The use of a novel microreactor system was also evaluated for the pinanol pyrolysis reaction. To our knowledge, this is the first time that a microreactor has been successfully used for this type of reaction in the Fragrance industry and a patent application is being filed by the CSIR. The kinetics of the reaction in both the tubular reactor system and the microreactor system was investigated. Computer modelling studies on both the systems were also conducted. The raw material cost to produce a kilogram of linalool is $1.40. There is a significant margin of 60.8 percent between the raw material cost of linalool and the current selling price ($3.57/kg). This clearly indicates that the project is potentially feasible from an economic point of view and we can now proceed with confidence to the next stage which is the engineering design, building and commissioning of the large scale pyrolysis rig. The rest of the process steps will be conducted on existing equipment currently present at the CSIR’s large scale facility (Imbiza in Isando, Gauteng).
- Full Text:
- Date Issued: 2009
The development of a commercial production process for p-menthane-3,8-diol
- Authors: Rust, Nico
- Date: 2009
- Subjects: Insect pests -- Control , Repellents
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10427 , http://hdl.handle.net/10948/d1018273
- Description: The synthesis of p-menthane-3,8-diol via the acid-catalyzed cyclization of citronellal in a dilute aqueous sulphuric acid medium was investigated using conventional batch and continuous systems in order to develop a commercial production process for said p-menthane-3,8-diol (PMD). The batch studies conducted during the first part of this study showed that the formation of PMD from citronellal occurs via an intra-molecular Prins reaction that results in the formation of both the desired PMD product, as well as the partially hydrated isopulegol. It was shown that the formationof the by- product, PMD-acetal, results from the reaction between an intermediate, 5-methyl-2- isopropylcyclohexanol, and the citronellal starting material, and not from the reaction between PMD and citronellal as previously reported. Kinetic studies confirmed the existence of a complicated kinetic model. The formation of PMD from citronellal displayed typical pseudo first order kinetics up to conversions of 70 after which the kinetic model becomes complicated as the result of the establishment of quasi equilibrium reactions between PMD and isopulegol (dehydration of PMD and hydration of isopulegol) and between PMD the PMD-acetal, both systems being acid catalysed. The PMD-acetal formation reaction appears to be second order with respect to PMD. Scale-up studies of the batch process to 30L and 50L scales showed that it would be extremely difficult to limit the level of PMD-acetal formation below the desired level of 1 percent, even if citronellal conversions are restricted to about 50 percent. During studies conducted on a commercially availablemicro-structured organic synthesis plant (OSP) it was shown that it is possible to perform the PMD reaction as a continuous process. The results obtained showed that the use of a micro-mixer such as the caterpillar micro-mixer did not provide enough residence time in order for desirable conversions (- 40 percent) to be obtained. By combining themicro-mixer with delay-loops of different thicknesses and lengths, and using increasing reaction temperatures, it was shown that the conversion of citronellal could be improved to some extent, but compared poorly to the expected conversions for a well-stirred batch reactor. By packing selected delay loops with inert SiC particles, improved mass transfer was observed between the organic and aqueous phases as reflected in the increased conversion of citronellal. Using the observations that were made during the use of the OSP, a continuous-flow, tubular reactor system was designed and constructed. Advanced statistical techniques were used to investigate the effect of variables such as temperature, acid concentration, reactor length, flow rate and the organic to aqueous ratio on the rate and selectivity of the reaction. Mathematical models were derived for citronellal conversion, yield of PMD and yield of PMD- acetals, and used to predict the concentrations of citronellal, PMD and PMD-acetals at set experimental conditions. The results obtained showed that it was possible to obtain a product which approached desired specifications.Downstream processing of the PMD reaction mixture as it exits the reactor requires phase separation and neutralization of the acid catalyst solution, followed by further work-up to recover unreacted starting material and intermediates for recycle back to the synthesis reactor, followed by purification of crude PMD to the desired specification. The study showed that neutralization, prior or after phase separation, does not affect the selectivity of the PMD to such a great extent, but does influence the relative conversion due to extended contact of the catalyst with the organic phase after the reaction is terminated. Recovery of unreacted citronellal and isopulegol could be achieved by a simple vacuum evaporation step, which may either be carried out in a batch manner using traditional distillation equipment, or in a continuous process using wiped-film (short path) techniques. It was also shown that selective crystallization of PMD from the crude product mixture by addition of a solvent, such as heptanes or hexane proved to be the best way of achieving the desired product specification.
- Full Text:
- Date Issued: 2009
- Authors: Rust, Nico
- Date: 2009
- Subjects: Insect pests -- Control , Repellents
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10427 , http://hdl.handle.net/10948/d1018273
- Description: The synthesis of p-menthane-3,8-diol via the acid-catalyzed cyclization of citronellal in a dilute aqueous sulphuric acid medium was investigated using conventional batch and continuous systems in order to develop a commercial production process for said p-menthane-3,8-diol (PMD). The batch studies conducted during the first part of this study showed that the formation of PMD from citronellal occurs via an intra-molecular Prins reaction that results in the formation of both the desired PMD product, as well as the partially hydrated isopulegol. It was shown that the formationof the by- product, PMD-acetal, results from the reaction between an intermediate, 5-methyl-2- isopropylcyclohexanol, and the citronellal starting material, and not from the reaction between PMD and citronellal as previously reported. Kinetic studies confirmed the existence of a complicated kinetic model. The formation of PMD from citronellal displayed typical pseudo first order kinetics up to conversions of 70 after which the kinetic model becomes complicated as the result of the establishment of quasi equilibrium reactions between PMD and isopulegol (dehydration of PMD and hydration of isopulegol) and between PMD the PMD-acetal, both systems being acid catalysed. The PMD-acetal formation reaction appears to be second order with respect to PMD. Scale-up studies of the batch process to 30L and 50L scales showed that it would be extremely difficult to limit the level of PMD-acetal formation below the desired level of 1 percent, even if citronellal conversions are restricted to about 50 percent. During studies conducted on a commercially availablemicro-structured organic synthesis plant (OSP) it was shown that it is possible to perform the PMD reaction as a continuous process. The results obtained showed that the use of a micro-mixer such as the caterpillar micro-mixer did not provide enough residence time in order for desirable conversions (- 40 percent) to be obtained. By combining themicro-mixer with delay-loops of different thicknesses and lengths, and using increasing reaction temperatures, it was shown that the conversion of citronellal could be improved to some extent, but compared poorly to the expected conversions for a well-stirred batch reactor. By packing selected delay loops with inert SiC particles, improved mass transfer was observed between the organic and aqueous phases as reflected in the increased conversion of citronellal. Using the observations that were made during the use of the OSP, a continuous-flow, tubular reactor system was designed and constructed. Advanced statistical techniques were used to investigate the effect of variables such as temperature, acid concentration, reactor length, flow rate and the organic to aqueous ratio on the rate and selectivity of the reaction. Mathematical models were derived for citronellal conversion, yield of PMD and yield of PMD- acetals, and used to predict the concentrations of citronellal, PMD and PMD-acetals at set experimental conditions. The results obtained showed that it was possible to obtain a product which approached desired specifications.Downstream processing of the PMD reaction mixture as it exits the reactor requires phase separation and neutralization of the acid catalyst solution, followed by further work-up to recover unreacted starting material and intermediates for recycle back to the synthesis reactor, followed by purification of crude PMD to the desired specification. The study showed that neutralization, prior or after phase separation, does not affect the selectivity of the PMD to such a great extent, but does influence the relative conversion due to extended contact of the catalyst with the organic phase after the reaction is terminated. Recovery of unreacted citronellal and isopulegol could be achieved by a simple vacuum evaporation step, which may either be carried out in a batch manner using traditional distillation equipment, or in a continuous process using wiped-film (short path) techniques. It was also shown that selective crystallization of PMD from the crude product mixture by addition of a solvent, such as heptanes or hexane proved to be the best way of achieving the desired product specification.
- Full Text:
- Date Issued: 2009
The selective dechlorination of poly-chlorophenols
- Authors: Thomas, Maxwell Paul
- Date: 2009
- Subjects: Sewage -- Purification -- Chlorination , Pesticides -- Toxicology , Chlorine -- Toxicology
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10391 , http://hdl.handle.net/10948/1124 , Sewage -- Purification -- Chlorination , Pesticides -- Toxicology , Chlorine -- Toxicology
- Description: Liquid phase catalytic hydrodechlorinations can provide a convenient and environmentally friendly method for treating organic chlorinated compounds in waste streams generated during the manufacturing of agrochemicals. During such treatment hydrochloric acid is generated as a by-product, which can be easily neutralized employing a base to yield an inorganic salt. This work describes the results obtained during the liquid phase hydrodechlorination of 2,6-dichlorophenol (2,6-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP). The hydrodechlorination of these chlorinated phenolic compounds in a mixture of methanol and water was investigated using supported and unsupported palladium catalysts to yield lower chlorinated phenols or phenol. Various parameters were investigated such as catalyst concentration, ammonium formate concentration, effect of base addition and effect of temperature. During this study two methods of hydrodechlorination were also investigated such as hydride-transfer hydrogenolysis, using ammonium formate, and hydrogenolysis, using dihydrogen. These methods offer a mild treatment in terms of the reaction temperature with temperatures used below 800C. A comparison of the palladium catalyst systems using these methods also showed that Pd/C produced the best results in terms of the hydrodechlorination rate and the selectivity towards phenol. When the ammonium formate method was used, complete hydrodechlorination of both substrates was achieved in 1h of reaction time at a selectivity of 100 percent towards phenol. A comparison of the method using dihydrogen and Pd/C showed that the reaction rate and the selectivity towards phenol during the hydrodechlorination of 2,6-DCP were 87.92 percent and 93.30 percent. Similarly, the reaction rate and selectivity during 2,4,6- TCP hydrodechlorination were 63.77 percent and 70.57 percent. These results were achieved in a reaction time of 3 hours. A high catalyst loading increases the reaction rate at the expense of selectivity, due to the formation of cyclohexanone, formed during further hydrogenation of phenol. The formation of cyclohexanone was limited at high temperatures (ca. 800C) with none detected during the hydrodechlorination of 2,6-DCP and 0.19 percent during the hydrodechlorination of 2,4,6-TCP. Evaluation of the hydrodechlorination parameters showed that the catalytic efficiency of the Pd/C catalysts was inhibited as the reaction proceeded due to the formation of HCl as by-product. A significant increase in the reaction rate was achieved when the reaction was performed in the presence of an inorganic base, which neutralized HCl.
- Full Text:
- Date Issued: 2009
- Authors: Thomas, Maxwell Paul
- Date: 2009
- Subjects: Sewage -- Purification -- Chlorination , Pesticides -- Toxicology , Chlorine -- Toxicology
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10391 , http://hdl.handle.net/10948/1124 , Sewage -- Purification -- Chlorination , Pesticides -- Toxicology , Chlorine -- Toxicology
- Description: Liquid phase catalytic hydrodechlorinations can provide a convenient and environmentally friendly method for treating organic chlorinated compounds in waste streams generated during the manufacturing of agrochemicals. During such treatment hydrochloric acid is generated as a by-product, which can be easily neutralized employing a base to yield an inorganic salt. This work describes the results obtained during the liquid phase hydrodechlorination of 2,6-dichlorophenol (2,6-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP). The hydrodechlorination of these chlorinated phenolic compounds in a mixture of methanol and water was investigated using supported and unsupported palladium catalysts to yield lower chlorinated phenols or phenol. Various parameters were investigated such as catalyst concentration, ammonium formate concentration, effect of base addition and effect of temperature. During this study two methods of hydrodechlorination were also investigated such as hydride-transfer hydrogenolysis, using ammonium formate, and hydrogenolysis, using dihydrogen. These methods offer a mild treatment in terms of the reaction temperature with temperatures used below 800C. A comparison of the palladium catalyst systems using these methods also showed that Pd/C produced the best results in terms of the hydrodechlorination rate and the selectivity towards phenol. When the ammonium formate method was used, complete hydrodechlorination of both substrates was achieved in 1h of reaction time at a selectivity of 100 percent towards phenol. A comparison of the method using dihydrogen and Pd/C showed that the reaction rate and the selectivity towards phenol during the hydrodechlorination of 2,6-DCP were 87.92 percent and 93.30 percent. Similarly, the reaction rate and selectivity during 2,4,6- TCP hydrodechlorination were 63.77 percent and 70.57 percent. These results were achieved in a reaction time of 3 hours. A high catalyst loading increases the reaction rate at the expense of selectivity, due to the formation of cyclohexanone, formed during further hydrogenation of phenol. The formation of cyclohexanone was limited at high temperatures (ca. 800C) with none detected during the hydrodechlorination of 2,6-DCP and 0.19 percent during the hydrodechlorination of 2,4,6-TCP. Evaluation of the hydrodechlorination parameters showed that the catalytic efficiency of the Pd/C catalysts was inhibited as the reaction proceeded due to the formation of HCl as by-product. A significant increase in the reaction rate was achieved when the reaction was performed in the presence of an inorganic base, which neutralized HCl.
- Full Text:
- Date Issued: 2009
Practical and scalable synthesis of N-Alkyl-N,N'Diacylhydrazines
- Authors: Gouws, Melissa Claire
- Date: 2008
- Subjects: Chemistry, Organic , Acylation , Insecticides
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10406 , http://hdl.handle.net/10948/696 , Chemistry, Organic , Acylation , Insecticides
- Description: The work presented in this thesis is concerned with the evaluation of potential synthetic routes for the diacylhydrazine group of compounds, and particularly, unsymmetrical diacylhydrazines. Diacylhydrazines form the basis for a relatively new group of insecticides that have molt accelerating properties, and which are considered to offer substantial advantages over other insecticides used for the control of certain insects. The overall objective for this study is to evaluate different potential synthetic routes for a model diacylhydrazine with the view to define potentially scaleable routes. The compound selected for this study was the unsymmetrical diacylhydrazine, N-[N-(tertbutyl) phenylcarbonylamino](4-methylphenyl)-carboxamide since it offers the same range of challenges that would be expected for the synthesis of other similar unsymmetrical diacylhydrazines. Thus, the synthesis of unsymmetrical diacylhydrazines require two reaction steps: The first step is the synthesis of the intermediate mono-acylhydrazine, while the second step is the synthesis of the desired diacylhydrazine from the intermediate mono-acylhydrazine. The most important factor in the two-step reaction sequence is to obtain a high degree of selectivity for the desired mono-acylhydrazine isomer. Acylation of t-butylhydrazine using 4-methylbenzoyl chloride can produce the desired product N-[(tert-butyl)amino](4-methylphenyl)carboxamide in yields above 90 percent, but this reaction produces a variety of by-products, including the “wrong” isomer (N-amino-N- (tert-butyl)(4-methylphenyl)carboximide). Unexpected byproducts for this particular acylation reaction, not previously reported in the literature have also been identified during this investigation. This includes a de-butylated diacylhydrazine, (4-methylphenyl)- N-[(4-methylphenyl)carbonylamino] carboxamide. Although the reaction between tert-butylhydrazine and 4-methylbenzaldehyde is very selective giving near quantitative yields of the desired hydrazone, the subsequent conversion of the hydrazone into the desired mono-acylhydrazine is problematic. The most promising route appears via bromination to form the hydrazidic bromide, followed by hydrolysis of the hydrazidic bromide. Yields for the bromination reaction during this investigation were somewhat higher than that reported previously in literature. Hydrolysis of the hydrazidic bromide, apparently also results in the hydrolysis of the reaction product to give an ester of the free acid (when an ester solvent is used). The synthesis of N-[N-(tert-butyl)phenylcarbonylamino](4-methyl phenyl)carboxamide was only briefly considered to evaluate essentially two approaches, namely: · The conversion of the monoacylhydrazine, N-[(tert-butyl)amino](4- methylphenyl)carboxamide, by acylating with either benzoyl chloride or methylbenzoate (gave 86 percent N-[N-(tert-butyl)phenylcarbonylamino](4-methyl phenyl)carboxamide when benzoyl chloride was used as acylating agent); and · The one-pot conversion of the hydrazone, [(1E)-2-(4-methylphenyl)-1- azavinyl](tert-butyl)]amine, by bromination/hydrolysis and acylation. In this case, benzoyl chloride (2 percent N-[N-(tert-butyl)phenylcarbonylamino](4-methyl phenyl)carboxamide), benzoic acid (80.67 percent N-[N-(tertbutyl) phenylcarbonylamino](4-methylphenyl)carboxamide) were evaluated as potential acylating agents.
- Full Text:
- Date Issued: 2008
- Authors: Gouws, Melissa Claire
- Date: 2008
- Subjects: Chemistry, Organic , Acylation , Insecticides
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10406 , http://hdl.handle.net/10948/696 , Chemistry, Organic , Acylation , Insecticides
- Description: The work presented in this thesis is concerned with the evaluation of potential synthetic routes for the diacylhydrazine group of compounds, and particularly, unsymmetrical diacylhydrazines. Diacylhydrazines form the basis for a relatively new group of insecticides that have molt accelerating properties, and which are considered to offer substantial advantages over other insecticides used for the control of certain insects. The overall objective for this study is to evaluate different potential synthetic routes for a model diacylhydrazine with the view to define potentially scaleable routes. The compound selected for this study was the unsymmetrical diacylhydrazine, N-[N-(tertbutyl) phenylcarbonylamino](4-methylphenyl)-carboxamide since it offers the same range of challenges that would be expected for the synthesis of other similar unsymmetrical diacylhydrazines. Thus, the synthesis of unsymmetrical diacylhydrazines require two reaction steps: The first step is the synthesis of the intermediate mono-acylhydrazine, while the second step is the synthesis of the desired diacylhydrazine from the intermediate mono-acylhydrazine. The most important factor in the two-step reaction sequence is to obtain a high degree of selectivity for the desired mono-acylhydrazine isomer. Acylation of t-butylhydrazine using 4-methylbenzoyl chloride can produce the desired product N-[(tert-butyl)amino](4-methylphenyl)carboxamide in yields above 90 percent, but this reaction produces a variety of by-products, including the “wrong” isomer (N-amino-N- (tert-butyl)(4-methylphenyl)carboximide). Unexpected byproducts for this particular acylation reaction, not previously reported in the literature have also been identified during this investigation. This includes a de-butylated diacylhydrazine, (4-methylphenyl)- N-[(4-methylphenyl)carbonylamino] carboxamide. Although the reaction between tert-butylhydrazine and 4-methylbenzaldehyde is very selective giving near quantitative yields of the desired hydrazone, the subsequent conversion of the hydrazone into the desired mono-acylhydrazine is problematic. The most promising route appears via bromination to form the hydrazidic bromide, followed by hydrolysis of the hydrazidic bromide. Yields for the bromination reaction during this investigation were somewhat higher than that reported previously in literature. Hydrolysis of the hydrazidic bromide, apparently also results in the hydrolysis of the reaction product to give an ester of the free acid (when an ester solvent is used). The synthesis of N-[N-(tert-butyl)phenylcarbonylamino](4-methyl phenyl)carboxamide was only briefly considered to evaluate essentially two approaches, namely: · The conversion of the monoacylhydrazine, N-[(tert-butyl)amino](4- methylphenyl)carboxamide, by acylating with either benzoyl chloride or methylbenzoate (gave 86 percent N-[N-(tert-butyl)phenylcarbonylamino](4-methyl phenyl)carboxamide when benzoyl chloride was used as acylating agent); and · The one-pot conversion of the hydrazone, [(1E)-2-(4-methylphenyl)-1- azavinyl](tert-butyl)]amine, by bromination/hydrolysis and acylation. In this case, benzoyl chloride (2 percent N-[N-(tert-butyl)phenylcarbonylamino](4-methyl phenyl)carboxamide), benzoic acid (80.67 percent N-[N-(tertbutyl) phenylcarbonylamino](4-methylphenyl)carboxamide) were evaluated as potential acylating agents.
- Full Text:
- Date Issued: 2008
Selective para-funtionalization of phenol
- Authors: Indurkar, Jayant R
- Date: 2008
- Subjects: Phenol
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10402 , http://hdl.handle.net/10948/710 , Phenol
- Description: In previous work done in our laboratories, a method was discovered to produce phenolic mono-ethers from 4-hydroxyacetophenone and other 4-hydroxyketones by treating with ammonium peroxy-disulfate in an alcohol as a reaction solvent and in the presence of concentrated sulphuric acid or other strong protonic acids. Since this method of producing 4-alkoxyphenol ethers provides a very convenient way to modify hydroquinone and substituted hydroquinones to produce a variety of phenol mono-ethers, it was of interest to study the general scope of this reaction, including a more detailed investigation of the reaction mechanism. In previous studies, it was suggested that interaction between the aromatic pi-system of hydroquinone and the cyclohexa-2,5-diene structure of benzoquinone plays a significant role during the reaction. It was therefore of interest to investigate whether other compounds that are also capable of forming the cyclohexa-2,5-diene structure, will interact in a manner analogous to the hydroquinone/benzoquinone couple. Two specific compounds were selected for this purpose, namely 4-nitrosophenol and 4- (diphenylmethylene)cyclohexa-2,5-dien-1-one . The scope of etherification reactions of hydroquinone-benzoquinone or hydroquinone/benzoquinone like substrates such as 4-nitrosophenol and 4- (diphenylmethylene)cyclohexa-2,5-dien-1-one in the presence of acid catalyst and alcohols was investigated. These studies showed that hydroquinone, 4- nitrosophenol and 4-(diphenylmethylene)cyclohexa-2,5-dien-1-one successfully affords the phenolic ethers in good to excellent yield. For example, quantitative yield of 4-methoxyphenol could be obtained from a 1:1 mixture of hydroquinone and benzoquinone at the reflux temperature of methanol. In order to study the reaction mechanism, the cross-over reaction between tertbutylhydroquinone and benzoquinone (or hydroquinone and tertbutylbenzoquinone) was studied in detail. The results of these cross-over reactions were used to propose a mechanistic pathway that could explain the requirement for pi-interaction between the hydroquinone and benzoquinone molecules, the role of the acid catalyst, as well as the relative rates of hydroquinone and benzoquinone consumption during these reactions. The mechanism was also capable of explaining all the reaction products observed during these reactions. The work was then extended to reactions of 4-nitrosophenol and 4- (diphenylmethylene)cyclohexa-2,5-dien-1-one with methanol in the presence of either hydroquinone or benzoquinone. The results of these investigations strongly suggest the presence of similar interactions between these molecules that also influence the outcome of the reactions. The exploitation of pi-interactions between two molecules of these types investigated during this work opens an interesting field of chemistry. Clearly, the level of understanding developed during this work is only beginning to address this interesting field of chemistry and much work will need to be done to gain a fuller understanding of the chemistry involved as well as the potential synthetic value of these interactions.
- Full Text:
- Date Issued: 2008
- Authors: Indurkar, Jayant R
- Date: 2008
- Subjects: Phenol
- Language: English
- Type: Thesis , Doctoral , DTech
- Identifier: vital:10402 , http://hdl.handle.net/10948/710 , Phenol
- Description: In previous work done in our laboratories, a method was discovered to produce phenolic mono-ethers from 4-hydroxyacetophenone and other 4-hydroxyketones by treating with ammonium peroxy-disulfate in an alcohol as a reaction solvent and in the presence of concentrated sulphuric acid or other strong protonic acids. Since this method of producing 4-alkoxyphenol ethers provides a very convenient way to modify hydroquinone and substituted hydroquinones to produce a variety of phenol mono-ethers, it was of interest to study the general scope of this reaction, including a more detailed investigation of the reaction mechanism. In previous studies, it was suggested that interaction between the aromatic pi-system of hydroquinone and the cyclohexa-2,5-diene structure of benzoquinone plays a significant role during the reaction. It was therefore of interest to investigate whether other compounds that are also capable of forming the cyclohexa-2,5-diene structure, will interact in a manner analogous to the hydroquinone/benzoquinone couple. Two specific compounds were selected for this purpose, namely 4-nitrosophenol and 4- (diphenylmethylene)cyclohexa-2,5-dien-1-one . The scope of etherification reactions of hydroquinone-benzoquinone or hydroquinone/benzoquinone like substrates such as 4-nitrosophenol and 4- (diphenylmethylene)cyclohexa-2,5-dien-1-one in the presence of acid catalyst and alcohols was investigated. These studies showed that hydroquinone, 4- nitrosophenol and 4-(diphenylmethylene)cyclohexa-2,5-dien-1-one successfully affords the phenolic ethers in good to excellent yield. For example, quantitative yield of 4-methoxyphenol could be obtained from a 1:1 mixture of hydroquinone and benzoquinone at the reflux temperature of methanol. In order to study the reaction mechanism, the cross-over reaction between tertbutylhydroquinone and benzoquinone (or hydroquinone and tertbutylbenzoquinone) was studied in detail. The results of these cross-over reactions were used to propose a mechanistic pathway that could explain the requirement for pi-interaction between the hydroquinone and benzoquinone molecules, the role of the acid catalyst, as well as the relative rates of hydroquinone and benzoquinone consumption during these reactions. The mechanism was also capable of explaining all the reaction products observed during these reactions. The work was then extended to reactions of 4-nitrosophenol and 4- (diphenylmethylene)cyclohexa-2,5-dien-1-one with methanol in the presence of either hydroquinone or benzoquinone. The results of these investigations strongly suggest the presence of similar interactions between these molecules that also influence the outcome of the reactions. The exploitation of pi-interactions between two molecules of these types investigated during this work opens an interesting field of chemistry. Clearly, the level of understanding developed during this work is only beginning to address this interesting field of chemistry and much work will need to be done to gain a fuller understanding of the chemistry involved as well as the potential synthetic value of these interactions.
- Full Text:
- Date Issued: 2008
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