The solvent-free approach versus the use of ionic liquids in the synthesis of ferrocenes
- Authors: Elago, Elago R T
- Date: 2008
- Subjects: Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10396 , http://hdl.handle.net/10948/853 , Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Description: The philosophy of green chemistry has seen much development in the past decade. The use of environmentally benign solvents is amongst the areas of green chemistry that have received the most attention. In this context, imidazolium ionic liquids have been widely reported to offer high product yields, fast reaction rates, excellent selectivity and generally mild working conditions, when used as reaction media. In addition, concerns about costs of solvents and the long-term environmental impact that can potentially result when solvents are discarded after their use have led to focused investigations into solvent-free procedures, as reported in recent literature. We have set out to explore the extent to which these advantages could be realized within our research. Non-volatile, non-flammable imidazolium ionic liquids [bmim][I], [bmim][BF4] and [bmim][PF6] were used as green solvents in ferrocene chemistry. Ferrocenoate esters were synthesised efficiently by the respective DCC/DMAP-promoted reactions of ferrocenecarboxylic acid and substituted benzoic acids or, alternatively, the DMAP-promoted reactions of ferrocenoyl fluoride with a range of substituted phenols in [bmim][BF4] and [bmim][PF6]. High yields and short reaction times were achieved. In addition, the ionic liquid was reused several times without a reduction in product yields. Under solvent-free conditions, DCC/DMAP-promoted reactions provided high yields within 3 min of reaction. The possible rearrangement of one of the intermediates in these reactions was modelled theoretically using density function theory (DFT) at the B3LYP/6-31G* level of approximation. Catalyst-free esterification was achieved by the application of microwave radiation to the reaction of ferrocenoyl fluoride and a range of substituted phenols. All the reactions were complete after 1 min of irradiation and products were isolated in high yield. DPAT, HfCl4, Sc(OTf)3 and Al(OTf)3 were screened as catalysts for esterification in [bmim][BF4] and under solvent-free conditions at various temperatures. All attempts at esterification of ferrocenecarboxylic acid with alcohols and phenols were unsuccessful. The Suzuki cross-coupling reaction was carried out in [bmim][BF4]. The isolated yields are, however, poor and suffer from poor reproducibility with different batches of [bmim][BF4] used.
- Full Text:
- Date Issued: 2008
- Authors: Elago, Elago R T
- Date: 2008
- Subjects: Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10396 , http://hdl.handle.net/10948/853 , Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Description: The philosophy of green chemistry has seen much development in the past decade. The use of environmentally benign solvents is amongst the areas of green chemistry that have received the most attention. In this context, imidazolium ionic liquids have been widely reported to offer high product yields, fast reaction rates, excellent selectivity and generally mild working conditions, when used as reaction media. In addition, concerns about costs of solvents and the long-term environmental impact that can potentially result when solvents are discarded after their use have led to focused investigations into solvent-free procedures, as reported in recent literature. We have set out to explore the extent to which these advantages could be realized within our research. Non-volatile, non-flammable imidazolium ionic liquids [bmim][I], [bmim][BF4] and [bmim][PF6] were used as green solvents in ferrocene chemistry. Ferrocenoate esters were synthesised efficiently by the respective DCC/DMAP-promoted reactions of ferrocenecarboxylic acid and substituted benzoic acids or, alternatively, the DMAP-promoted reactions of ferrocenoyl fluoride with a range of substituted phenols in [bmim][BF4] and [bmim][PF6]. High yields and short reaction times were achieved. In addition, the ionic liquid was reused several times without a reduction in product yields. Under solvent-free conditions, DCC/DMAP-promoted reactions provided high yields within 3 min of reaction. The possible rearrangement of one of the intermediates in these reactions was modelled theoretically using density function theory (DFT) at the B3LYP/6-31G* level of approximation. Catalyst-free esterification was achieved by the application of microwave radiation to the reaction of ferrocenoyl fluoride and a range of substituted phenols. All the reactions were complete after 1 min of irradiation and products were isolated in high yield. DPAT, HfCl4, Sc(OTf)3 and Al(OTf)3 were screened as catalysts for esterification in [bmim][BF4] and under solvent-free conditions at various temperatures. All attempts at esterification of ferrocenecarboxylic acid with alcohols and phenols were unsuccessful. The Suzuki cross-coupling reaction was carried out in [bmim][BF4]. The isolated yields are, however, poor and suffer from poor reproducibility with different batches of [bmim][BF4] used.
- Full Text:
- Date Issued: 2008
Ionic liquids as media for electro-organic synthesis
- Authors: Kruger, Elna
- Date: 2007
- Subjects: Ionic solutions , Inorganic compounds -- Synthesis , Electrochemistry
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10413 , http://hdl.handle.net/10948/538 , Ionic solutions , Inorganic compounds -- Synthesis , Electrochemistry
- Description: The IL’s used in this study were either synthesized or commercially available. Preparation of the IL’s involved 2 step processes: firstly the heating of distilled 1-methylimidazole with distilled 1-chlorobutane under reflux to obtain 1-butyl-3- methylimidazolium chloride; secondly, the metathesis reaction of sodium tetrafluoroborate with 1-butyl-3-methylimidazolium chloride to obtain 1-butyl-3- methylimidazolium tetrafluoroborate. The addition of sodium tetrafluoroborate, sodium hexafluorophosphate and lithium trifluoromethane sulfonamide with 1-butyl-3-methylimidazolium chloride produced good yields of 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide respectively. The IL’s are hygroscopic and must be stored under a nitrogen atmosphere. The IL’s were analyzed using 1H and 13C NMR analysis with CDCl3 as solvent. The physical and chemical properties of these IL’s were compared to commercial products. The physical and chemical properties compared well to reference values from the literature. The physical properties measured include the density, conductivity and electrochemical window. The electrochemical window is dependant primarily on the resistance of the cation to reduction and the resistance of the anion to oxidation. The electrochemical windows of the IL’s were very similar to the reference windows obtained from literature and it can be seen that some IL’s have a slightly lower window which can be due to water present. Water content in the IL’s was determined with the use of a Karl Fischer titrator, with Hydranal 5 Composite as titrant and HPLC grade methanol as the base. The concentration of halide in the IL’s was determined with a Perkin-Elmer ICP-MS.
- Full Text:
- Date Issued: 2007
- Authors: Kruger, Elna
- Date: 2007
- Subjects: Ionic solutions , Inorganic compounds -- Synthesis , Electrochemistry
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10413 , http://hdl.handle.net/10948/538 , Ionic solutions , Inorganic compounds -- Synthesis , Electrochemistry
- Description: The IL’s used in this study were either synthesized or commercially available. Preparation of the IL’s involved 2 step processes: firstly the heating of distilled 1-methylimidazole with distilled 1-chlorobutane under reflux to obtain 1-butyl-3- methylimidazolium chloride; secondly, the metathesis reaction of sodium tetrafluoroborate with 1-butyl-3-methylimidazolium chloride to obtain 1-butyl-3- methylimidazolium tetrafluoroborate. The addition of sodium tetrafluoroborate, sodium hexafluorophosphate and lithium trifluoromethane sulfonamide with 1-butyl-3-methylimidazolium chloride produced good yields of 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide respectively. The IL’s are hygroscopic and must be stored under a nitrogen atmosphere. The IL’s were analyzed using 1H and 13C NMR analysis with CDCl3 as solvent. The physical and chemical properties of these IL’s were compared to commercial products. The physical and chemical properties compared well to reference values from the literature. The physical properties measured include the density, conductivity and electrochemical window. The electrochemical window is dependant primarily on the resistance of the cation to reduction and the resistance of the anion to oxidation. The electrochemical windows of the IL’s were very similar to the reference windows obtained from literature and it can be seen that some IL’s have a slightly lower window which can be due to water present. Water content in the IL’s was determined with the use of a Karl Fischer titrator, with Hydranal 5 Composite as titrant and HPLC grade methanol as the base. The concentration of halide in the IL’s was determined with a Perkin-Elmer ICP-MS.
- Full Text:
- Date Issued: 2007
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