Aluminium triflate as a Lewis acid catalyst in some epoxide and aromatic transformations
- Authors: Lawton, Michelle Claire
- Date: 2012-03-14
- Subjects: Lewis acids , Aluminum , Alcoholysis , Epoxy compounds , Catalysts , Aromatic compounds , Substitution reactions
- Type: Thesis
- Identifier: http://ujcontent.uj.ac.za8080/10210/368554 , uj:2163 , http://hdl.handle.net/10210/4536
- Description: M.Sc. , Lewis acids play an important role in catalysis; they are associated with mild conditions, high selectivities and unique reactivities. Traditional Lewis acids such as AlCb and BF3 successfully catalyse such well known reactions as the Friedel-Crafts acylation reaction, Aldol condensation reactions and many more. These catalysts, however, must be used in a stoichiometric amount and are destroyed during the aqueous workup procedures. Lately, there has been a lot of interest in the role of metal triflate as Lewis acid catalysts. They were found to be effective in a wide range of reactions when used in catalytic amounts. They were also found to be recyclable and reusable without the loss of activity. Most of this research has been centred around the lanthanide triflates as well as scandium, bismuth and yttrium triflates. Very little research has been done using aluminium triflate and this triflate forms the focus ofthis study. The work contained in this dissertation demonstrates that Al(OTf)3 is an efficient catalyst for the ring opening of a variety of epoxides by alcohols when present in only ppm amounts. These reactions provided products in very high yields and selectivities. Simple acyclic and cyclic epoxides readily underwent ring opening reactions with a range of alcohols, typically providing the monoglycol ethers as single compounds (from the cyclic epoxides) or as mixtures of the two possible glycol monoethers (from the acyclic epoxides). In the case of styrene oxide, essentially a single compound was isolated. In contrast, the glycidyl ethers required slightly higher catalyst loadings before similar rates and conversions to product were observed. Additionally, an interesting selectivity was observed in the orientation of the attack of the alcohol onto the epoxide, which appeared to be chelation controlled. Similarly, the Al(OTf)3 also catalysed the aminolysis of a variety of epoxides. These reactions proceeded smoothly with catalytic amounts of the triflate present, and served to nicely highlight the role that steric and electronic factors played in these reactions. A preliminary study was carried out into the efficacy of Al(OTf)3 as a catalyst for Friedel-Crafts acylation and aromatic nitration reactions. From these studies it is evident that the Al(OTf)3 is indeed an effective catalyst for these reactions when present in substoichiometric levels and further studies will be carried out in this area in the future.
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Intermolecular dynamics between aromatic compounds and ester polymeric solvents
- Authors: Scheepers, Jacques J. , Muzenda, Edison , Belaid, Mohamed
- Date: 2013
- Subjects: Activity coefficients , Aromatic compounds , Solubility , Esters
- Type: Article
- Identifier: uj:4836 , http://hdl.handle.net/10210/12484
- Description: This work focused on the interactions that occur between ester solvents and simple aromatic solutes. Solutes were selected from various functional groups in their simplest form, and predictions of activity coefficients at infinite dilution were made using the Modified UNIFAC Dortmund group contribution model. The model computation was set up on a Microsoft Excel spreadsheet specifically designed for this purpose. For polar aromatic solutes, solubility decreased with increase in size of the ester solvent molecule and the opposite was found to be true for non-polar solutes. For all aromatic/ ester solvent interactions there was a decrease in activity coefficients with an increase in the degree of ester unsaturation.
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Aromatic compounds and ester polymeric solvents interactions
- Authors: Muzenda, Edison
- Date: 2014
- Subjects: Activity coefficients , Aromatic compounds , Esters , Solubility , Volatile organic compounds
- Type: Article
- Identifier: uj:4771 , ISSN 2320–4087 , http://hdl.handle.net/10210/11946
- Description: This work focused on the interactions that occur between ester polymeric solvents and simple aromatic volatile organic compounds (VOCs). Solutes were selected from various functional groups in their simplest form and computations of infinite dilution activity coefficients were performed using the Modified UNIFAC Dortmund group contribution model using a Microsoft Excel spreadsheet designed for this purpose. For polar aromatic VOCs, solubility decreased with increase in size of the ester solvent molecule and the opposite behavior was observed for non-polar VOCs. For all aromatic - ester solvent interactions, solubility increased with the increase in the degree of ester unsaturation.
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Oksidasie van suikers en aromatiese verbindings met dimetieldioksiraan
- Authors: Siemens, Hester
- Date: 2014-04-15
- Subjects: Aromatic compounds , Sugars , Oxidation , Quinone
- Type: Thesis
- Identifier: uj:10679 , http://hdl.handle.net/10210/10195
- Description: M.Sc. (Chemistry) , The aim of this study was to investigate the oxidation of aromatic compounds and benzylidene acetals with dimethyldioxinne. Dimethyldioxirane, either by Insitu preparation or in the isolated form, has shown remarkable reactivity. This oxidant is effective in oxygen transfer, readily prepared from commercial materials and reacts under mild conditions. Quinones are natural materials with biological activity and some are key intermediates in the synthesis of medicines. A well-known method for the preparation of quinones, is the oxidation of phenols and aromatic ethers. The oxidation of simple phenol and anisole derivatives by dimethyldioxirane yielded complex mixtures. More hindered aromatic compounds were investigated, since the oxidation of these compounds proceeded in a more controlled manner. In this study the phenols were found to be more reactive than the corresponding aromatic ethers. para-Quinones were formed preferentially, whereas ortho-quinones were observed in one or two cases. Products formed in these oxidations depend on the substitution pattern of the substrate. The oxidation of phenols and aromatic compounds formed complex mixtures and does not have many synthetic applications. Mechanisms are proposed for the formation of the different products. Benzylidene acetals are important protecting groups in the chemistry of carbohydrates. Cleavage of these benzylidene acetals gave either the free diol or benzyl ether or benzoyl ester, depending on the reagent used. The reaction of dimethyldioxirane with benzylidene acetals gave the benzoylesters. With dioxanes, e.g. 4,6-O-benzylidene sugar derivatives, there are no difference in stereoelectronic effects in the cleavage of C-4 and C-6. The major product has a 6-benzoate group, probably due to the greater stability of the primary benzoate. In dioxolanes both reactivity and regioselectivity of the reactions are influenced by stereoeleetronic effects. It has been found that the cleavage of dioxolanes took place preferably in a conformation where the oxygen is antiperiplanar towards the leaving group. It has been shown that dimethyldioxinme can be used with success in the deprotection of benzylidene acetals in the chemistry of carbohydrates.
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