Asymmetric induction in reactions of chiral carboxylic esters and silyl enol ethers
- Authors: Evans, Melanie Daryl
- Date: 1998
- Subjects: Ethers -- Synthesis Esters -- Synthesis Chirality Asymmetric synthesis Organic compounds -- Synthesis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4409 , http://hdl.handle.net/10962/d1006762
- Description: Several camphor and pinane derivatives have been synthesised and evaluated for use as chiral auxiliaries in asymmetric synthesis. Various blocking groups have been attached to the camphor skeleton in attempts to improve stereofacial selectivity; these include α-methoxybenzyl and xylyl groups, and novel stereoisomeric ketal moieties derived from meso- and (R,R)-(-)-2,3-butanediol. Benzylation reactions carried out on the lithium enolates of ester derivatives of the camphor-derived chiral auxiliaries afforded α-benzylated products in 5-60% diastereomeric excess. Stereochemical aspects have been explored using high resolution NMR, X-ray crystallographic and computer modelling techniques, and hydrolysis of selected α-benzylated products has permitted the diasteroselective bias to be confirmed. Opposite configurations at the new stereogenic centre are clearly favoured by the xylyl and ketal blocking groups - an observation rationalised in terms of the presence or absence of chelating potential in the blocking group. Baylis-Hillman reactions carried out on a series of specially prepared camphor-derived acrylic esters containing the ketal blocking group exhibited both low diastereoselectivities (0-30% d.e.) and very long reaction times. Chiral silyl enol ethers, synthesised using both pinane and camphor derivatives as chiral auxiliaries, showed up to 20% diastereomeric excess in MCPBA oxidation, alkylation and Mukaiyama reactions. Attempts to bring the prochiral centre in the silyl enol ether substrates closer to the chiral auxiliary, and thus improve the stereofacial selectivity, proved unsuccessful. The silyl enol ether derivatives, however, display interesting fragmentation patterns in their electron impact mass spectra, which were investigated using a combination of high resolution MS, comparative low resolution MS and metastable peak analysis.
- Full Text:
- Date Issued: 1998
- Authors: Evans, Melanie Daryl
- Date: 1998
- Subjects: Ethers -- Synthesis Esters -- Synthesis Chirality Asymmetric synthesis Organic compounds -- Synthesis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4409 , http://hdl.handle.net/10962/d1006762
- Description: Several camphor and pinane derivatives have been synthesised and evaluated for use as chiral auxiliaries in asymmetric synthesis. Various blocking groups have been attached to the camphor skeleton in attempts to improve stereofacial selectivity; these include α-methoxybenzyl and xylyl groups, and novel stereoisomeric ketal moieties derived from meso- and (R,R)-(-)-2,3-butanediol. Benzylation reactions carried out on the lithium enolates of ester derivatives of the camphor-derived chiral auxiliaries afforded α-benzylated products in 5-60% diastereomeric excess. Stereochemical aspects have been explored using high resolution NMR, X-ray crystallographic and computer modelling techniques, and hydrolysis of selected α-benzylated products has permitted the diasteroselective bias to be confirmed. Opposite configurations at the new stereogenic centre are clearly favoured by the xylyl and ketal blocking groups - an observation rationalised in terms of the presence or absence of chelating potential in the blocking group. Baylis-Hillman reactions carried out on a series of specially prepared camphor-derived acrylic esters containing the ketal blocking group exhibited both low diastereoselectivities (0-30% d.e.) and very long reaction times. Chiral silyl enol ethers, synthesised using both pinane and camphor derivatives as chiral auxiliaries, showed up to 20% diastereomeric excess in MCPBA oxidation, alkylation and Mukaiyama reactions. Attempts to bring the prochiral centre in the silyl enol ether substrates closer to the chiral auxiliary, and thus improve the stereofacial selectivity, proved unsuccessful. The silyl enol ether derivatives, however, display interesting fragmentation patterns in their electron impact mass spectra, which were investigated using a combination of high resolution MS, comparative low resolution MS and metastable peak analysis.
- Full Text:
- Date Issued: 1998
Baylis-Hillman derived benzopyrans and related systems : a synthetic and mechanistic study
- Authors: Robinson, Ross Stuart
- Date: 1998
- Subjects: Benzopyrans Coumarins Heterocyclic compounds -- Derivatives
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4429 , http://hdl.handle.net/10962/d1007193
- Description: The Baylis-Hillman reaction between substituted salicylaldehydes and various acrylate species has been shown to afford complex reaction mixtures, careful chromatography of which has led to the isolation of an extensive range of novel compounds. One- and two-dimensional NMR spectroscopic, mass spectrometric and X-ray crystallographic analysis of these compounds have permitted identification of no less than eight general classes of chromene and coumarin derivatives. The formation of the various product types is attributed to cascades of successive reactions stemming, in each case, from a Baylis-Hillman product as the common intermediate. The mechanistic sequence involved in the formation of the various chromene and coumarin derivatives have been elucidated by examining isolated or specifically prepared compounds as putative reaction intermediates. Conjugate addition and acyl or allylic substitution by various nucleophiles appear to be common processes in the formation of the chromene and coumarin derivatives, and studies focussing on these processes have been undertaken. Reactions of Baylis-Hillman adducts have been carried out, using oxygen, sulfur and nitrogen nucleophiles, in order to explore stereoselectivity and regioselectivity trends. The results show that the reactions proceed with a very high degree of regioselectivity, affording conjugate addition rather than acyl substitution products. The diastereoselectivity observed for the addition products, however was typically low. A kinetic study to explore the regioselectivity of the reaction between various Baylis-Hillman derived halogeno esters and the nucleophile, methyl 3-oxobutanolate enloate, in two different base-solvent systems at high dilution was also undertaken. The reactions were monitored by ¹H NMR spectroscopy, and the results revealed that the reaction kinetics are more complex than originally anticipated. A mechanistic rationalisation is offered which is consistent with both the kinetic data and the observed regioselectivity trends.
- Full Text:
- Date Issued: 1998
- Authors: Robinson, Ross Stuart
- Date: 1998
- Subjects: Benzopyrans Coumarins Heterocyclic compounds -- Derivatives
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4429 , http://hdl.handle.net/10962/d1007193
- Description: The Baylis-Hillman reaction between substituted salicylaldehydes and various acrylate species has been shown to afford complex reaction mixtures, careful chromatography of which has led to the isolation of an extensive range of novel compounds. One- and two-dimensional NMR spectroscopic, mass spectrometric and X-ray crystallographic analysis of these compounds have permitted identification of no less than eight general classes of chromene and coumarin derivatives. The formation of the various product types is attributed to cascades of successive reactions stemming, in each case, from a Baylis-Hillman product as the common intermediate. The mechanistic sequence involved in the formation of the various chromene and coumarin derivatives have been elucidated by examining isolated or specifically prepared compounds as putative reaction intermediates. Conjugate addition and acyl or allylic substitution by various nucleophiles appear to be common processes in the formation of the chromene and coumarin derivatives, and studies focussing on these processes have been undertaken. Reactions of Baylis-Hillman adducts have been carried out, using oxygen, sulfur and nitrogen nucleophiles, in order to explore stereoselectivity and regioselectivity trends. The results show that the reactions proceed with a very high degree of regioselectivity, affording conjugate addition rather than acyl substitution products. The diastereoselectivity observed for the addition products, however was typically low. A kinetic study to explore the regioselectivity of the reaction between various Baylis-Hillman derived halogeno esters and the nucleophile, methyl 3-oxobutanolate enloate, in two different base-solvent systems at high dilution was also undertaken. The reactions were monitored by ¹H NMR spectroscopy, and the results revealed that the reaction kinetics are more complex than originally anticipated. A mechanistic rationalisation is offered which is consistent with both the kinetic data and the observed regioselectivity trends.
- Full Text:
- Date Issued: 1998
Camphor-derived chiral auxiliaries in asymmetric synthesis
- Authors: Molema, Warner Evert
- Date: 1998
- Subjects: Asymmetric synthesis Chirality Camphor
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4417 , http://hdl.handle.net/10962/d1006848
- Description: The investigation has been focussed largely on the chemistry and stereo-directing potential of camphor-derived compounds. The major regioisomer produced on partial hydrolysis of N-benzylcamphorimide was identified, by one- and two-dimensional NMR and X-ray crystallography, as (+)-(1S,3R)-(N-enzylcarbamoyl)-2,3,3-trimethylcyclopentanecarboxylic acid, the methyl ester of which was shown to undergo an unexpected intramolecular rearrangement during LAH reduction to afford (1S,3R)-Nbenzyl-3-hydroxymethyl-2,2,3-trimethylcyclopentane carboxamide. Several tartrate- and camphor-derived diols have been investigated as chiral auxiliaries in various asymmetric reactions of corresponding acetals of α,β-unsaturated aldehydes. MCPBA epoxidation of the tartrate-derived acetals afforded epoxy acetals in 4-12% diastereomeric excess. The camphor-derived acetals were obtained solely as the exosubstituted diastereomers, the stereochemistry being confirmed by two-dimensional NMR spectroscopy and X-ray crystallography. Simmons-Smith cyclopropanation of these camphor-derived acetals afforded cyclopropyl products with diastereoselectivities of 4% d.e. for the bornane-2,10-diol acetal and 46->99% d.e. for the bomane-2,3-diol acetals. In order to increase diastereofacial selectivity, a camphor-derived diol having a bulky substituent at C-10 was prepared, viz., phenyl 2,3-dihydroxybomane-10sulfonate, and α,β-unsaturated acetals of this diol were shown to undergo Simmons-Smith cyclopropanation with complete topological control (>99% d.e.), the diastereoselectivities being conveniently determined by ¹H and ¹³C NMR spectroscopy. Computer modelling, with the software package HYPERCHEM®, was used to explore the stereochemical aspects of the Simmons-Smith cyclopropanation, and hydrolysis of one of the cyclopropyl acetals has permitted the diastereoselective bias to be confirmed. (+)-Pinane-2,3-diol was also investigated as a chiral auxiliary in the Simmons-Smith reactions of α,β-unsaturated aldehydes, and moderate diastereoselectivities (20-30% d.e.) were observed. In a series of exploratory studies, the Diels-Alder reaction of the 2,3-dihydroxybomane-10-sulfonate acetal of trans-cinnamaldehyde with cyclopentadiene afforded a single cycloadduct, while OSO₄ dihydroxylation, MCPBA oxidation and alkylation of chiral acetals produced from both bomane-2,3-diol and phenyl 2,3-dihydroxybomane-10-sulfonate were less selective.
- Full Text:
- Date Issued: 1998
- Authors: Molema, Warner Evert
- Date: 1998
- Subjects: Asymmetric synthesis Chirality Camphor
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4417 , http://hdl.handle.net/10962/d1006848
- Description: The investigation has been focussed largely on the chemistry and stereo-directing potential of camphor-derived compounds. The major regioisomer produced on partial hydrolysis of N-benzylcamphorimide was identified, by one- and two-dimensional NMR and X-ray crystallography, as (+)-(1S,3R)-(N-enzylcarbamoyl)-2,3,3-trimethylcyclopentanecarboxylic acid, the methyl ester of which was shown to undergo an unexpected intramolecular rearrangement during LAH reduction to afford (1S,3R)-Nbenzyl-3-hydroxymethyl-2,2,3-trimethylcyclopentane carboxamide. Several tartrate- and camphor-derived diols have been investigated as chiral auxiliaries in various asymmetric reactions of corresponding acetals of α,β-unsaturated aldehydes. MCPBA epoxidation of the tartrate-derived acetals afforded epoxy acetals in 4-12% diastereomeric excess. The camphor-derived acetals were obtained solely as the exosubstituted diastereomers, the stereochemistry being confirmed by two-dimensional NMR spectroscopy and X-ray crystallography. Simmons-Smith cyclopropanation of these camphor-derived acetals afforded cyclopropyl products with diastereoselectivities of 4% d.e. for the bornane-2,10-diol acetal and 46->99% d.e. for the bomane-2,3-diol acetals. In order to increase diastereofacial selectivity, a camphor-derived diol having a bulky substituent at C-10 was prepared, viz., phenyl 2,3-dihydroxybomane-10sulfonate, and α,β-unsaturated acetals of this diol were shown to undergo Simmons-Smith cyclopropanation with complete topological control (>99% d.e.), the diastereoselectivities being conveniently determined by ¹H and ¹³C NMR spectroscopy. Computer modelling, with the software package HYPERCHEM®, was used to explore the stereochemical aspects of the Simmons-Smith cyclopropanation, and hydrolysis of one of the cyclopropyl acetals has permitted the diastereoselective bias to be confirmed. (+)-Pinane-2,3-diol was also investigated as a chiral auxiliary in the Simmons-Smith reactions of α,β-unsaturated aldehydes, and moderate diastereoselectivities (20-30% d.e.) were observed. In a series of exploratory studies, the Diels-Alder reaction of the 2,3-dihydroxybomane-10-sulfonate acetal of trans-cinnamaldehyde with cyclopentadiene afforded a single cycloadduct, while OSO₄ dihydroxylation, MCPBA oxidation and alkylation of chiral acetals produced from both bomane-2,3-diol and phenyl 2,3-dihydroxybomane-10-sulfonate were less selective.
- Full Text:
- Date Issued: 1998
Homogenous and heterogenous catalytic activity of metallophthalocyanines towards electrochemical detection of organic compounds
- Authors: Mafatle, Tsukutlane J P
- Date: 1998
- Subjects: Electrochemistry , Organic compounds , Phenols
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4316 , http://hdl.handle.net/10962/d1004974 , Electrochemistry , Organic compounds , Phenols
- Description: Cysteine plays an important role in many biological and pharmaceutical systems. Therefore, in view of its importance, it is essential to find means of detecting it at the lowest possible levels. In this regard, electrochemical techniques have been found to be capable of detecting analytes even at micro levels. However, electrochemical determination of cysteine occurs at a very high potentials. These overpotentials makes quantitative analysis or detection of cysteine difficult at most conventional carbon electrodes. On platinum electrode, the oxidation of cysteine has been reported to occur in the potential range 0.7 to 1.45 V (vs NHE). Therefore, the object of this investigative study has been to find an active complex that could replace platinum and other expensive metals as electrodes. Such a complex should also be capable of reducing the potential at which the oxidation of cysteine occurs on carbon electrodes. As a result, this manuscript gives a full report on the investigative study of electrocatalytic activity of molybdenum phthalocyanine complexes towards detection of cysteine. Molybdenum phthalocyanine, OMo(OH)Pc, and its tetrasulfonated derivative, [OMo(OH)TSPc]⁴⁻ were successfully used to reduce the potential needed to initiate the oxidation of cysteine on carbon paste electrodes (CPE). The oxidation of cysteine on CPE modified with [OMo(OH)Pc]⁴⁻ was found to occur at 0.29 V (vs Ag/AgCl), and in the presence of [OMo(OH)TSPc]⁴⁻ species in solution the oxidation occurred at 0.33 V (vs Ag/AgCl). Molybdenum, in the oxidation states of Mo(IV), Mo(V) and Mo(VI), is found in biological systems as an essential trace element, participating in a number of enzymatic reactions, where it is believed to be coordinated to sulphur-containing ligands in many molybdenum enzymes. This therefore explains why molybdenum phthalocyanines were employed in electroanalytical detection of sulphur containing amino acid, cysteine. Electrochemical methods have also been successfully used in detection of environmental pollutants such as phenolic compounds. Phenolic compounds are oxidised at readily accessible potentials. However, like cysteine, there are problems associated with the electrochemical detection of these important environmental pollutants. Their electrooxidation is known to form dimeric and/or polymeric oxidation products which adsorb onto the electrode surface, thus -videactivating it. Therefore, to address this problem, cobalt phthalocyanine (CoPc) and its tetrasulfonated derivative, [CoTSPc]⁴⁻ were employed in electrocatalytic detection of phenolic compounds. These complexes were found to increase the anodic peak currents for the oxidation of o-cresol, m-cresol, p-cresol, phenol, 2-chlorophenol and 4-chlorophenol. In addition, CoPc deposited onto the glassy carbon electrode improved the stability of the electrode, by reducing electrode poisoning caused by the electrooxidation products of the mentioned phenolic compounds. The potential at which the oxidation occurred and the current response of individual phenolic compounds depended on the degree of substitution and the type of substituent on the phenol molecule. In general, the current response was found to be lower for chlorinated phenols compared with the cresols and phenol. To establish the role of the central metal in the catalytic process, comparison of the electrocatalytic activity of some of the first row transition metal phthalocyanines, for the detection of mono-substituted phenolic compounds, showed the following trend: Co⁽¹¹⁾ > Mn⁽¹¹⁾ > Fe⁽¹¹⁾Pc > Ni⁽¹¹⁾Pc > Cu⁽¹¹⁾Pc > H₂Pc > Zn⁽¹¹⁾Pc > Bare GCE. A report is also given on electrocatalysis using [CoTSPc]⁴⁻ electrochemically deposited on the glassy carbon electrode. This was also found to enhance the anodic peak currents for the oxidation of all phenolic compounds. A report on the effects of scan rate, operating potential, analyte concentration and other variables is also given.
- Full Text:
- Date Issued: 1998
- Authors: Mafatle, Tsukutlane J P
- Date: 1998
- Subjects: Electrochemistry , Organic compounds , Phenols
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4316 , http://hdl.handle.net/10962/d1004974 , Electrochemistry , Organic compounds , Phenols
- Description: Cysteine plays an important role in many biological and pharmaceutical systems. Therefore, in view of its importance, it is essential to find means of detecting it at the lowest possible levels. In this regard, electrochemical techniques have been found to be capable of detecting analytes even at micro levels. However, electrochemical determination of cysteine occurs at a very high potentials. These overpotentials makes quantitative analysis or detection of cysteine difficult at most conventional carbon electrodes. On platinum electrode, the oxidation of cysteine has been reported to occur in the potential range 0.7 to 1.45 V (vs NHE). Therefore, the object of this investigative study has been to find an active complex that could replace platinum and other expensive metals as electrodes. Such a complex should also be capable of reducing the potential at which the oxidation of cysteine occurs on carbon electrodes. As a result, this manuscript gives a full report on the investigative study of electrocatalytic activity of molybdenum phthalocyanine complexes towards detection of cysteine. Molybdenum phthalocyanine, OMo(OH)Pc, and its tetrasulfonated derivative, [OMo(OH)TSPc]⁴⁻ were successfully used to reduce the potential needed to initiate the oxidation of cysteine on carbon paste electrodes (CPE). The oxidation of cysteine on CPE modified with [OMo(OH)Pc]⁴⁻ was found to occur at 0.29 V (vs Ag/AgCl), and in the presence of [OMo(OH)TSPc]⁴⁻ species in solution the oxidation occurred at 0.33 V (vs Ag/AgCl). Molybdenum, in the oxidation states of Mo(IV), Mo(V) and Mo(VI), is found in biological systems as an essential trace element, participating in a number of enzymatic reactions, where it is believed to be coordinated to sulphur-containing ligands in many molybdenum enzymes. This therefore explains why molybdenum phthalocyanines were employed in electroanalytical detection of sulphur containing amino acid, cysteine. Electrochemical methods have also been successfully used in detection of environmental pollutants such as phenolic compounds. Phenolic compounds are oxidised at readily accessible potentials. However, like cysteine, there are problems associated with the electrochemical detection of these important environmental pollutants. Their electrooxidation is known to form dimeric and/or polymeric oxidation products which adsorb onto the electrode surface, thus -videactivating it. Therefore, to address this problem, cobalt phthalocyanine (CoPc) and its tetrasulfonated derivative, [CoTSPc]⁴⁻ were employed in electrocatalytic detection of phenolic compounds. These complexes were found to increase the anodic peak currents for the oxidation of o-cresol, m-cresol, p-cresol, phenol, 2-chlorophenol and 4-chlorophenol. In addition, CoPc deposited onto the glassy carbon electrode improved the stability of the electrode, by reducing electrode poisoning caused by the electrooxidation products of the mentioned phenolic compounds. The potential at which the oxidation occurred and the current response of individual phenolic compounds depended on the degree of substitution and the type of substituent on the phenol molecule. In general, the current response was found to be lower for chlorinated phenols compared with the cresols and phenol. To establish the role of the central metal in the catalytic process, comparison of the electrocatalytic activity of some of the first row transition metal phthalocyanines, for the detection of mono-substituted phenolic compounds, showed the following trend: Co⁽¹¹⁾ > Mn⁽¹¹⁾ > Fe⁽¹¹⁾Pc > Ni⁽¹¹⁾Pc > Cu⁽¹¹⁾Pc > H₂Pc > Zn⁽¹¹⁾Pc > Bare GCE. A report is also given on electrocatalysis using [CoTSPc]⁴⁻ electrochemically deposited on the glassy carbon electrode. This was also found to enhance the anodic peak currents for the oxidation of all phenolic compounds. A report on the effects of scan rate, operating potential, analyte concentration and other variables is also given.
- Full Text:
- Date Issued: 1998
Chemical studies of necic acid analogues
- Guthrie-Strachan, Jeffry James
- Authors: Guthrie-Strachan, Jeffry James
- Date: 1997
- Subjects: Organic acids , Chemistry, Organic
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4425 , http://hdl.handle.net/10962/d1006909 , Organic acids , Chemistry, Organic
- Description: Various aldehydes have been reacted with methyl acrylate under Baylis-Hillman conditions, using DABCO as a catalyst, to afford a range of α-substituted acrylic esters containing an allylic hydroxy group. Selected Baylis-Hillman products have been brominated, hydrolysed and acetylated to afford substrates for the synthesis of necic acid analogues. The diastereo- and regioselectivity of nucleophilic attack, using sodium methylmercaptan, on the Baylis-Hillman products and selected brominated derivatives was investigated. The allylic hydroxy compounds favour conjugate addition with the generation of a new chiral centre, while the allylic bromo derivatives favour substitution (SN and SN') (S[subscript N] and S[subscript N]') with consequent loss of chirality. (E)-2-Isopropylcrotonic acid, a vital precursor in the synthesis of all stereoisomers of trachelanthic and viridifloric acid, was synthesised in an attempt to obtain the necic acid components required for total alkaloid synthesis of lycopsamine and its derivatives. This precursor and salicylic acid were then used to prepare esters of retronecine, a dihydroxy necine base obtained via extraction and consequent hydrolysis of retrorsine.
- Full Text:
- Date Issued: 1997
- Authors: Guthrie-Strachan, Jeffry James
- Date: 1997
- Subjects: Organic acids , Chemistry, Organic
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4425 , http://hdl.handle.net/10962/d1006909 , Organic acids , Chemistry, Organic
- Description: Various aldehydes have been reacted with methyl acrylate under Baylis-Hillman conditions, using DABCO as a catalyst, to afford a range of α-substituted acrylic esters containing an allylic hydroxy group. Selected Baylis-Hillman products have been brominated, hydrolysed and acetylated to afford substrates for the synthesis of necic acid analogues. The diastereo- and regioselectivity of nucleophilic attack, using sodium methylmercaptan, on the Baylis-Hillman products and selected brominated derivatives was investigated. The allylic hydroxy compounds favour conjugate addition with the generation of a new chiral centre, while the allylic bromo derivatives favour substitution (SN and SN') (S[subscript N] and S[subscript N]') with consequent loss of chirality. (E)-2-Isopropylcrotonic acid, a vital precursor in the synthesis of all stereoisomers of trachelanthic and viridifloric acid, was synthesised in an attempt to obtain the necic acid components required for total alkaloid synthesis of lycopsamine and its derivatives. This precursor and salicylic acid were then used to prepare esters of retronecine, a dihydroxy necine base obtained via extraction and consequent hydrolysis of retrorsine.
- Full Text:
- Date Issued: 1997
Design, synthesis and evaluation of novel, metal complexing agents
- Authors: Hagemann, Justin Philip
- Date: 1997
- Subjects: Ligands Metal complexes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4307 , http://hdl.handle.net/10962/d1004965
- Description: Various chelating ligands have been designed and synthesised; these include amino-amide ligands, tetraacetic acid systems and sulfur-containing amide ligands. Difficulties in the synthesis and purification of the amino-amide ligands were largely overcome, permitting the mono acylation of ethylenediamine and the synthesis of bis(2-aminoethyl)-2-benzylpropanediamide. Novel tetraacetic acid ligands, based on the propanediamide backbone and targeted as EDTA analogues, were obtained from their methyl and benzyl esters; but the instability of the tetraacids prevented their full characterisation. Bidentate, tridentate and tetradentate sulfur-containing monoamide ligands, based on the ortho-thio acetanilide moiety, were designed to specifically chelate platinum and palladium in the presence of base metals. In their synthesis, thiocyanation was used to introduce the orth-thio group on para-substituted anilines, and further functionalisation was achieved via appropriate protection of nucleophilic sulfur moieties. A range of tetradentate, sulfur-containing diamide ligands was also synthesised by reacting substituted 2-mercaptoacetanilides with 1,2- dibromoethane. Novel ligands were characterised by spectroscopic (¹H and ¹³C NMR; IR and M S) techniques and elemental (combustion and high resolution MS) analysis. Computer modelling and ¹H NMR chemical shift data have been used to explore the conformational preferences of the sulfur-containing acetanilide ligands. The macrocyclic ligands and systems with ortho-methylthio substituents appear to exhibit the greatest degree of coplanarity of the aromatic and amide functions. Solvent extraction studies revealed that the sulfur-containing amide ligands selectively extracted palladium(II) from platinum(II), copper(II}, nickel(II} and cobalt(II}. Even though the palladium(II} was extracted from an acidic medium, certain monoamide ligands were able to complex palladium(II) through their sulfur and deprotonated amide nitrogen donors, a trithia monoamide ligand being observed to displace all the chloride ligands on palladium to form a monomeric tetracoordinate complex. The diamide ligands, however, appeared to favour extraction of palladium(II) by coordination through their sulfur donors, forming 5-membered sulfur-sulfur chelates. In basic media (pH 8-9), selected sulfur-containing monoamide and diamide ligands have been shown to complex platinum(II) and palladium(II) through their sulfur and deprotonated amide nitrogen donors. At neutral pH, a dimercapto monoamide ligand has been shown to complex platinum from cisplatin with partial expulsion of the ammine ligands, while a macrocyclic trithia monoamide ligand has been observed to complex platinum from tetrachloroplatinate with concomitant deprotonation of the amide nitrogen. Where possible, the complexes were characterised by infrared and ¹H NMR spectroscopy and have also been studied using the computer modelling soft-ware programmes, Momec® and Hyperchem®.
- Full Text:
- Date Issued: 1997
- Authors: Hagemann, Justin Philip
- Date: 1997
- Subjects: Ligands Metal complexes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4307 , http://hdl.handle.net/10962/d1004965
- Description: Various chelating ligands have been designed and synthesised; these include amino-amide ligands, tetraacetic acid systems and sulfur-containing amide ligands. Difficulties in the synthesis and purification of the amino-amide ligands were largely overcome, permitting the mono acylation of ethylenediamine and the synthesis of bis(2-aminoethyl)-2-benzylpropanediamide. Novel tetraacetic acid ligands, based on the propanediamide backbone and targeted as EDTA analogues, were obtained from their methyl and benzyl esters; but the instability of the tetraacids prevented their full characterisation. Bidentate, tridentate and tetradentate sulfur-containing monoamide ligands, based on the ortho-thio acetanilide moiety, were designed to specifically chelate platinum and palladium in the presence of base metals. In their synthesis, thiocyanation was used to introduce the orth-thio group on para-substituted anilines, and further functionalisation was achieved via appropriate protection of nucleophilic sulfur moieties. A range of tetradentate, sulfur-containing diamide ligands was also synthesised by reacting substituted 2-mercaptoacetanilides with 1,2- dibromoethane. Novel ligands were characterised by spectroscopic (¹H and ¹³C NMR; IR and M S) techniques and elemental (combustion and high resolution MS) analysis. Computer modelling and ¹H NMR chemical shift data have been used to explore the conformational preferences of the sulfur-containing acetanilide ligands. The macrocyclic ligands and systems with ortho-methylthio substituents appear to exhibit the greatest degree of coplanarity of the aromatic and amide functions. Solvent extraction studies revealed that the sulfur-containing amide ligands selectively extracted palladium(II) from platinum(II), copper(II}, nickel(II} and cobalt(II}. Even though the palladium(II} was extracted from an acidic medium, certain monoamide ligands were able to complex palladium(II) through their sulfur and deprotonated amide nitrogen donors, a trithia monoamide ligand being observed to displace all the chloride ligands on palladium to form a monomeric tetracoordinate complex. The diamide ligands, however, appeared to favour extraction of palladium(II) by coordination through their sulfur donors, forming 5-membered sulfur-sulfur chelates. In basic media (pH 8-9), selected sulfur-containing monoamide and diamide ligands have been shown to complex platinum(II) and palladium(II) through their sulfur and deprotonated amide nitrogen donors. At neutral pH, a dimercapto monoamide ligand has been shown to complex platinum from cisplatin with partial expulsion of the ammine ligands, while a macrocyclic trithia monoamide ligand has been observed to complex platinum from tetrachloroplatinate with concomitant deprotonation of the amide nitrogen. Where possible, the complexes were characterised by infrared and ¹H NMR spectroscopy and have also been studied using the computer modelling soft-ware programmes, Momec® and Hyperchem®.
- Full Text:
- Date Issued: 1997
Solid state thermal decomposition of amide complexes of nickel(II) chloride
- Nelwamondo, Aubrey Ndifelani
- Authors: Nelwamondo, Aubrey Ndifelani
- Date: 1997
- Subjects: Decomposition (Chemistry) Materials -- Thermal properties Amides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4345 , http://hdl.handle.net/10962/d1005008
- Description: The thermal decompositions of a series of amide complexes of nickel(II) chloride have been studied. Thermochemical, kinetic, structure and solid-state stability correlations have been investigated. Complexes containing homologous amide ligands (L) of the form NiLCℓ₂, Ni₃L₂Cℓ₆, Ni₃LCℓ₆, NiL₂Cℓ₂(2H₂0) and ML₂Cℓ₂ (where M = Ni(II), Co(II) or Cu(II)) have been prepared. Chemical analysis, spectral and thermogravimetric measurements were used to characterize the complexes and their decomposition stoichiometries. Three sets of reactions were identified as yielding stable products in a single step: (i) NiLCℓ₂ (s) → NiCℓ₂ (s) + L (g) (ii) Ni₃LCℓ₆ (s) → 3NiCℓ₂ (s) + 2L (g) (iii) Ni₃LCℓ₆ (s) → 3NiCℓ₂ (s) + L (g) Characterization of the processes in the ML₂Cℓ₂ and NiL₂Cℓ₂(2H₂0) complexes was not straightforward. Reaction enthalpies (ΔH) were determined using DSC. The orders of the reaction onset temperatures (Tc), peak temperatures (Tmax) and ΔHL values for the NiCℓ₂ system were: N-methylacetamide < acetamide < N-methylformamide, suggesting the importance of steric hindrance of the methyl-substituent groups in the amide skeleton. In the Ni₃LCℓ₆, NiL₂Cℓ₂(2H₂0) and ML₂Cℓ₂ systems no simple orders could be deduced. The Te and Tmax sequences obtained from analogous metal(II) chloride complexes indicated that the copper(II) complexes were the least stable. The kinetics of the loss of L from NiLCℓ₂ complexes were investigated using isothermal TG, non-isothermal TG and DSC measurements. The contracting geometry models described the course of the decompositions in the most satisfactory manner. Apparent activation energies ( Ea) were estimated from Arrhenius plots of rate coefficients from: (i) an approximate zero-order relationship, (ii) the contracting-area (R2) and contracting-volume (R3) equations, (iii) a new empirical (B2) expression, (iv) the half-life ( 1/t₀.₅) and (v) the characteristic feature of the rate-time curve ( 1/tmax/2 ). The non-dependence of Ea on the rate equation used supports the reliability of the kinetic parameters. Non-isothermal experiments were analyzed by the Coats-Redfern, the modified BorchardtDaniels and the Kissinger methods. Arrhenius parameters were in keeping with results from the isothermal kinetic measurements. The values of Ea obtained for the NiLCℓ₂ system increased with an increase in basicity of the amide ligands. No straightforward correlation was found between Ea and Te, Tmax, ΔHL or spectral properties.
- Full Text:
- Date Issued: 1997
- Authors: Nelwamondo, Aubrey Ndifelani
- Date: 1997
- Subjects: Decomposition (Chemistry) Materials -- Thermal properties Amides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4345 , http://hdl.handle.net/10962/d1005008
- Description: The thermal decompositions of a series of amide complexes of nickel(II) chloride have been studied. Thermochemical, kinetic, structure and solid-state stability correlations have been investigated. Complexes containing homologous amide ligands (L) of the form NiLCℓ₂, Ni₃L₂Cℓ₆, Ni₃LCℓ₆, NiL₂Cℓ₂(2H₂0) and ML₂Cℓ₂ (where M = Ni(II), Co(II) or Cu(II)) have been prepared. Chemical analysis, spectral and thermogravimetric measurements were used to characterize the complexes and their decomposition stoichiometries. Three sets of reactions were identified as yielding stable products in a single step: (i) NiLCℓ₂ (s) → NiCℓ₂ (s) + L (g) (ii) Ni₃LCℓ₆ (s) → 3NiCℓ₂ (s) + 2L (g) (iii) Ni₃LCℓ₆ (s) → 3NiCℓ₂ (s) + L (g) Characterization of the processes in the ML₂Cℓ₂ and NiL₂Cℓ₂(2H₂0) complexes was not straightforward. Reaction enthalpies (ΔH) were determined using DSC. The orders of the reaction onset temperatures (Tc), peak temperatures (Tmax) and ΔHL values for the NiCℓ₂ system were: N-methylacetamide < acetamide < N-methylformamide, suggesting the importance of steric hindrance of the methyl-substituent groups in the amide skeleton. In the Ni₃LCℓ₆, NiL₂Cℓ₂(2H₂0) and ML₂Cℓ₂ systems no simple orders could be deduced. The Te and Tmax sequences obtained from analogous metal(II) chloride complexes indicated that the copper(II) complexes were the least stable. The kinetics of the loss of L from NiLCℓ₂ complexes were investigated using isothermal TG, non-isothermal TG and DSC measurements. The contracting geometry models described the course of the decompositions in the most satisfactory manner. Apparent activation energies ( Ea) were estimated from Arrhenius plots of rate coefficients from: (i) an approximate zero-order relationship, (ii) the contracting-area (R2) and contracting-volume (R3) equations, (iii) a new empirical (B2) expression, (iv) the half-life ( 1/t₀.₅) and (v) the characteristic feature of the rate-time curve ( 1/tmax/2 ). The non-dependence of Ea on the rate equation used supports the reliability of the kinetic parameters. Non-isothermal experiments were analyzed by the Coats-Redfern, the modified BorchardtDaniels and the Kissinger methods. Arrhenius parameters were in keeping with results from the isothermal kinetic measurements. The values of Ea obtained for the NiLCℓ₂ system increased with an increase in basicity of the amide ligands. No straightforward correlation was found between Ea and Te, Tmax, ΔHL or spectral properties.
- Full Text:
- Date Issued: 1997
Structural and stereochemical investigations of terrestrial and marine pyrone metabolites
- Authors: Collett, Lynne Alison
- Date: 1997
- Subjects: Metabolites , Stereochemistry , Siphonaria
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4348 , http://hdl.handle.net/10962/d1005013 , Metabolites , Stereochemistry , Siphonaria
- Description: This thesis presents an investigation into the chemistry of 6 substituted 5, 6-dihydro-a-pyrone compounds. A comprehensive review of these compounds was published in 1989 and the subsequent literature is covered in an updated review presented below. Eight 6-substituted 5,6-dihydro-a-pyrone metabolites from three different South African plant species Cryptocarya latijolia, Syncolostemon densiflorus, and Syncolostemon argenteus have been the subject of structural and stereochemical investigations. The absolute stereochemistry of the known compound "triacetate" from C. latijolia has been established as 6R-[2R,4S,6S-(triacetyloxy)heptylJ-5,6-dihydro-2H-pyran-2-one (74) using CD and acetonide formation with subsequent application of the modified Moshers method. The absolute stereochemistry of the related metabolite "diacetate", also from C. latijolia, has been assigned as 6R-[2S,4S-diacetyloxypentylJ-5,6-dihydro-2H-pyran-2-one (76). In addition, the outstanding stereochemistry at C-5' in syndenolide, from S. densiflorus, followed from conversion to its diacetonide and subsequent NMR analysis. Syndenolide is therefore 6R-[5S-(acetoxy)-IR,2R,3S-(trihydroxy)-heptylJ-5,6- dihydro-2H -pyran-2-one. The genus Syncolostemon has proved to be a rich source of a-pyrone compounds and the chemistry of S. argenteus, not investigated previously, was examined as part of an ongoing search for new 5,6-dihydro-a-pyrones. The study yielded five new a-pyrone natural products, synargentolide A-E. The structure of synargentolide A (82) has been assigned as 6R[4R,5R,6S-triacetyloxy-lE-heptenylJ-5,6-dihydro-2H-pyran-2-one using CD and NMR techniques. The structures of synargentolide B (87), C (92) and E (94) also followed from a detailed NMR analysis and the stereochemistry tentatively assigned based on CD and NMR data. Synargentolide D (93) was thermally unstable, and a paucity of material prevented stereochemical investigations, however the structure was determined from initial NMR analysis. The marine molluscs of the genus Siphonaria have only become the subject of chemical studies in the last fifteen years. These molluscs characteristically produce polypropionate type natural products. A review of Siphonarian polypropionate metabolites containing a pyrone functionality is presented. Examination of an endemic South African species Siphonaria serrata yielded one novel polypropionate metabolite containing a ),-pyrone functionality, siserrone A (131). The structure of this compound was unambiguously established using standard NMR experiments. The relative stereochemisty of the hemi-ketal moiety was assigned from a careful analysis of the ROESY NMR spectrum and the stereochemisty of the acyclic portion determined from a comparison of the 13C and 'H NMR data of a degradation product with the corresponding data of a synthetic compound. It was also established that the modified Moshers method could not be used to determine the absolute stereochemistry of the secondary hydroxy I substituent at C-11. The absolute stereochemistry of 131 was thus assigned in accordance with the proven stereochemistry of Siphonarian metabolites.
- Full Text:
- Date Issued: 1997
- Authors: Collett, Lynne Alison
- Date: 1997
- Subjects: Metabolites , Stereochemistry , Siphonaria
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4348 , http://hdl.handle.net/10962/d1005013 , Metabolites , Stereochemistry , Siphonaria
- Description: This thesis presents an investigation into the chemistry of 6 substituted 5, 6-dihydro-a-pyrone compounds. A comprehensive review of these compounds was published in 1989 and the subsequent literature is covered in an updated review presented below. Eight 6-substituted 5,6-dihydro-a-pyrone metabolites from three different South African plant species Cryptocarya latijolia, Syncolostemon densiflorus, and Syncolostemon argenteus have been the subject of structural and stereochemical investigations. The absolute stereochemistry of the known compound "triacetate" from C. latijolia has been established as 6R-[2R,4S,6S-(triacetyloxy)heptylJ-5,6-dihydro-2H-pyran-2-one (74) using CD and acetonide formation with subsequent application of the modified Moshers method. The absolute stereochemistry of the related metabolite "diacetate", also from C. latijolia, has been assigned as 6R-[2S,4S-diacetyloxypentylJ-5,6-dihydro-2H-pyran-2-one (76). In addition, the outstanding stereochemistry at C-5' in syndenolide, from S. densiflorus, followed from conversion to its diacetonide and subsequent NMR analysis. Syndenolide is therefore 6R-[5S-(acetoxy)-IR,2R,3S-(trihydroxy)-heptylJ-5,6- dihydro-2H -pyran-2-one. The genus Syncolostemon has proved to be a rich source of a-pyrone compounds and the chemistry of S. argenteus, not investigated previously, was examined as part of an ongoing search for new 5,6-dihydro-a-pyrones. The study yielded five new a-pyrone natural products, synargentolide A-E. The structure of synargentolide A (82) has been assigned as 6R[4R,5R,6S-triacetyloxy-lE-heptenylJ-5,6-dihydro-2H-pyran-2-one using CD and NMR techniques. The structures of synargentolide B (87), C (92) and E (94) also followed from a detailed NMR analysis and the stereochemistry tentatively assigned based on CD and NMR data. Synargentolide D (93) was thermally unstable, and a paucity of material prevented stereochemical investigations, however the structure was determined from initial NMR analysis. The marine molluscs of the genus Siphonaria have only become the subject of chemical studies in the last fifteen years. These molluscs characteristically produce polypropionate type natural products. A review of Siphonarian polypropionate metabolites containing a pyrone functionality is presented. Examination of an endemic South African species Siphonaria serrata yielded one novel polypropionate metabolite containing a ),-pyrone functionality, siserrone A (131). The structure of this compound was unambiguously established using standard NMR experiments. The relative stereochemisty of the hemi-ketal moiety was assigned from a careful analysis of the ROESY NMR spectrum and the stereochemisty of the acyclic portion determined from a comparison of the 13C and 'H NMR data of a degradation product with the corresponding data of a synthetic compound. It was also established that the modified Moshers method could not be used to determine the absolute stereochemistry of the secondary hydroxy I substituent at C-11. The absolute stereochemistry of 131 was thus assigned in accordance with the proven stereochemistry of Siphonarian metabolites.
- Full Text:
- Date Issued: 1997
Synthetic and physical organic studies of chromone derivatives
- Ramaite, Ipfani David Isaiah
- Authors: Ramaite, Ipfani David Isaiah
- Date: 1997
- Subjects: Benzopyrans Heterocyclic compounds -- Derivatives Coumarins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4380 , http://hdl.handle.net/10962/d1005045
- Description: A range of chromone-2-carboxylic acids has been prepared by condensing suitably substituted 2-hydroxyacetophenones with diethyl oxalate. pK₂ Studies of these acids revealed that 6- or 7-methoxy substituents decreased acidity while the 6-nitro group enhanced acidity; the strongest acid was the 3-chloro derivative, the increase in acidity being attributed to steric inhibition of acid-weakening delocalisation between the carboxyl group and the chromone system. Various chromone-2-carboxamides, derived from acid chloride precursors, were converted to polysubstituted acrylamides by nucleophilic ring-opening with selected amine nucleophiles. The main fragmentation patterns exhibited by these acrylamides were elucidated using a combination of low resolution, high resolution and meta-stable peak analysis, while the effect of substituents on the simultaneous internal rotation involving the carboxamide and enamine moieties were studied using dynamic NMR spectroscopy. Rotational barriers of ca. 67.1 kJmol ̄¹ and ca. 102 kJmol ̄¹ were found for the enamine and amide rotors, respectively. Several synthetic pathways were followed to prepare a series of 2-(N,N-dialkylamino)chromones which were subjected to detailed mass spectral analysis. In addition to substituent-specific fragmentations , the 2-aminochromones appear to fragment via 3 major pathways. The effect of substituents on the internal rotation of the amino moeity was investigated by variable temperature ¹H NMR spectroscopy and the resulting DNMR data was used to calculate the rotational barriers. Examination of the data reveals that the electron-releasing 6- and 7- substituents reduce the C-NMe₂ rotational barrier to ca. 43.5 kJmol ̄¹ , while the nitro analogue has the largest rotational barrier (ca. 46.1 kJmol ̄¹) because of the electron-withdrawing effect of this substituent.
- Full Text:
- Date Issued: 1997
- Authors: Ramaite, Ipfani David Isaiah
- Date: 1997
- Subjects: Benzopyrans Heterocyclic compounds -- Derivatives Coumarins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4380 , http://hdl.handle.net/10962/d1005045
- Description: A range of chromone-2-carboxylic acids has been prepared by condensing suitably substituted 2-hydroxyacetophenones with diethyl oxalate. pK₂ Studies of these acids revealed that 6- or 7-methoxy substituents decreased acidity while the 6-nitro group enhanced acidity; the strongest acid was the 3-chloro derivative, the increase in acidity being attributed to steric inhibition of acid-weakening delocalisation between the carboxyl group and the chromone system. Various chromone-2-carboxamides, derived from acid chloride precursors, were converted to polysubstituted acrylamides by nucleophilic ring-opening with selected amine nucleophiles. The main fragmentation patterns exhibited by these acrylamides were elucidated using a combination of low resolution, high resolution and meta-stable peak analysis, while the effect of substituents on the simultaneous internal rotation involving the carboxamide and enamine moieties were studied using dynamic NMR spectroscopy. Rotational barriers of ca. 67.1 kJmol ̄¹ and ca. 102 kJmol ̄¹ were found for the enamine and amide rotors, respectively. Several synthetic pathways were followed to prepare a series of 2-(N,N-dialkylamino)chromones which were subjected to detailed mass spectral analysis. In addition to substituent-specific fragmentations , the 2-aminochromones appear to fragment via 3 major pathways. The effect of substituents on the internal rotation of the amino moeity was investigated by variable temperature ¹H NMR spectroscopy and the resulting DNMR data was used to calculate the rotational barriers. Examination of the data reveals that the electron-releasing 6- and 7- substituents reduce the C-NMe₂ rotational barrier to ca. 43.5 kJmol ̄¹ , while the nitro analogue has the largest rotational barrier (ca. 46.1 kJmol ̄¹) because of the electron-withdrawing effect of this substituent.
- Full Text:
- Date Issued: 1997
Computer modelling of pyrotechnic combustion
- Authors: Taylor, Steven John
- Date: 1996
- Subjects: Combustion -- Computer simulation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4426 , http://hdl.handle.net/10962/d1006913
- Description: One of the most important industrial uses of pyrotechnic compositions is as delay fuses in electric detonators. Many factors influence the rate of burning of such fuses. These include (a) the primary choice of chemical components, followed by (b) the physical properties of these components, particularly the particle-size and distribution of the fuel, (c) the composition of the system chosen and (d) the presence of additives and/or impurities. A full experimental study of the influences of even a few of these factors, while attempting to hold other potential variables constant, would be extremely time consuming and hence attention has been focused on the possibilities of modelling pyrotechnic combustion. Various approaches to the modelling of pyrotechnic combustion are discussed. These include:- (i) one-dimensional finite-difference models; (ii) two-dimensional finite-element models; (iii) particle-packing considerations; (iv) Monte Carlo models. Predicted behaviour is compared with extensive experimental information for the widely-used antimony/potassium permanganate pyrotechnic system, and the tungsten /potassium dichromate pyrotechnic system. The one-dimensional finite-difference model was investigated to give a simple means of investigating the effects of some parameters on the combustion of a pyrotechnic. The two-dimensional finite-difference model used similar inputs, but at the expense of considerably more computer power, gave more extensive information such as the shape of the burning front and the temperature gradients throughout the column and within the casing material. Both these models gave improved results when allowance was made for autocatalytic kinetics in place of the usual assumption of an "order-of-reaction", n ≤ 1. The particle-packing model investigated the qualitative relationship between the maximum burning rate of a pyrotechnic system and the maximum number of contact points (per 1.00 g composition) calculated for that system. Qualitative agreement was found for those systems which are presumed to burn mainly via solid-solid reactions. The Monte Carlo model investigated the effect of the random packing of fuel and oxidant particles on the variability of the burning rate of a pyrotechnic composition.
- Full Text:
- Date Issued: 1996
- Authors: Taylor, Steven John
- Date: 1996
- Subjects: Combustion -- Computer simulation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4426 , http://hdl.handle.net/10962/d1006913
- Description: One of the most important industrial uses of pyrotechnic compositions is as delay fuses in electric detonators. Many factors influence the rate of burning of such fuses. These include (a) the primary choice of chemical components, followed by (b) the physical properties of these components, particularly the particle-size and distribution of the fuel, (c) the composition of the system chosen and (d) the presence of additives and/or impurities. A full experimental study of the influences of even a few of these factors, while attempting to hold other potential variables constant, would be extremely time consuming and hence attention has been focused on the possibilities of modelling pyrotechnic combustion. Various approaches to the modelling of pyrotechnic combustion are discussed. These include:- (i) one-dimensional finite-difference models; (ii) two-dimensional finite-element models; (iii) particle-packing considerations; (iv) Monte Carlo models. Predicted behaviour is compared with extensive experimental information for the widely-used antimony/potassium permanganate pyrotechnic system, and the tungsten /potassium dichromate pyrotechnic system. The one-dimensional finite-difference model was investigated to give a simple means of investigating the effects of some parameters on the combustion of a pyrotechnic. The two-dimensional finite-difference model used similar inputs, but at the expense of considerably more computer power, gave more extensive information such as the shape of the burning front and the temperature gradients throughout the column and within the casing material. Both these models gave improved results when allowance was made for autocatalytic kinetics in place of the usual assumption of an "order-of-reaction", n ≤ 1. The particle-packing model investigated the qualitative relationship between the maximum burning rate of a pyrotechnic system and the maximum number of contact points (per 1.00 g composition) calculated for that system. Qualitative agreement was found for those systems which are presumed to burn mainly via solid-solid reactions. The Monte Carlo model investigated the effect of the random packing of fuel and oxidant particles on the variability of the burning rate of a pyrotechnic composition.
- Full Text:
- Date Issued: 1996
Computer modelling of the thermal decomposition of solids
- Authors: De la Croix, Annemarie
- Date: 1996
- Subjects: Solids -- Thermal properties -- Computer simulation
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4302 , http://hdl.handle.net/10962/d1004960 , Solids -- Thermal properties -- Computer simulation
- Description: Decompositions of solids are typically of the form: A(s) ----> B(s) + gases. Symmetry-controlled routes (based on known and hypothetical crystal structures) for transforming the solid reactant into the solid product were devised as possible decomposition pathways. Lattice energies of the reactants, of the postulated transient intermediate structures and of the final solid products were then estimated by crystal modelling procedures. Profiles of lattice energy changes during the proposed decomposition routes were constructed and any energy barriers were compared with experimental activation energies reported for the thermal decompositions. The crystal modelling was performed with the computer program WMIN. Calculation of the lattice energies involved the development of a model potential for the perfect lattice and the evaluation of the interatomic parameters. The potential was based on the Born model of ionic solids using the Buckingham potential (Ø(r)= Ae⁻r/p - C/r⁶) to describe the short-range energy contribution. Empirical fitting was used to establish reliable interatomic energy parameters. The reliability of the interatomic potentials was assessed by calculating crystal structures and lattice energies (which were not included in the fitting). The particular reactions selected for modelling were the decompositions of the alkaline-earth metal (Ca, Sr, Ba) peroxides and carbonates: M0₂(s) ---> MO(s) + ¹/₂0₂(g) MC0₃(s) ---> MO(s) + CO₂(g)The lattice energies calculated for the known structures were in good agreement with reported values, (except for Ba0₂ and BaC0₃) which provided support for the adequacy of the potential model used. Activation energies calculated for the decomposition of the carbonates were in the correct order but hlgher than experimental values, i. e., 422, 422, 465 and 499 kJ mol̄̄⁻¹ compared to the experimental values of 205, 87(?), 222 and 283 kJ mol̄̄⁻¹ for CaC0₃ (calcite), CaC0₃(aragonite), SrC0₃ and BaC0₃. The values calculated for the peroxides (91 and 100 kJ mol⁻¹ compared to the experimental values of 119 and 185 kJ mol⁻¹ for Sr0₂ and Ba0₂ respectively) were less satisfactory but could be a reflection of the poor structural data used for the peroxides. The significance of this approach to the modelling of solid decompositions is discussed.
- Full Text:
- Date Issued: 1996
- Authors: De la Croix, Annemarie
- Date: 1996
- Subjects: Solids -- Thermal properties -- Computer simulation
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4302 , http://hdl.handle.net/10962/d1004960 , Solids -- Thermal properties -- Computer simulation
- Description: Decompositions of solids are typically of the form: A(s) ----> B(s) + gases. Symmetry-controlled routes (based on known and hypothetical crystal structures) for transforming the solid reactant into the solid product were devised as possible decomposition pathways. Lattice energies of the reactants, of the postulated transient intermediate structures and of the final solid products were then estimated by crystal modelling procedures. Profiles of lattice energy changes during the proposed decomposition routes were constructed and any energy barriers were compared with experimental activation energies reported for the thermal decompositions. The crystal modelling was performed with the computer program WMIN. Calculation of the lattice energies involved the development of a model potential for the perfect lattice and the evaluation of the interatomic parameters. The potential was based on the Born model of ionic solids using the Buckingham potential (Ø(r)= Ae⁻r/p - C/r⁶) to describe the short-range energy contribution. Empirical fitting was used to establish reliable interatomic energy parameters. The reliability of the interatomic potentials was assessed by calculating crystal structures and lattice energies (which were not included in the fitting). The particular reactions selected for modelling were the decompositions of the alkaline-earth metal (Ca, Sr, Ba) peroxides and carbonates: M0₂(s) ---> MO(s) + ¹/₂0₂(g) MC0₃(s) ---> MO(s) + CO₂(g)The lattice energies calculated for the known structures were in good agreement with reported values, (except for Ba0₂ and BaC0₃) which provided support for the adequacy of the potential model used. Activation energies calculated for the decomposition of the carbonates were in the correct order but hlgher than experimental values, i. e., 422, 422, 465 and 499 kJ mol̄̄⁻¹ compared to the experimental values of 205, 87(?), 222 and 283 kJ mol̄̄⁻¹ for CaC0₃ (calcite), CaC0₃(aragonite), SrC0₃ and BaC0₃. The values calculated for the peroxides (91 and 100 kJ mol⁻¹ compared to the experimental values of 119 and 185 kJ mol⁻¹ for Sr0₂ and Ba0₂ respectively) were less satisfactory but could be a reflection of the poor structural data used for the peroxides. The significance of this approach to the modelling of solid decompositions is discussed.
- Full Text:
- Date Issued: 1996
Reduction of tungsten oxides with carbon and hydrogen
- Authors: Venables, Dean Stuart
- Date: 1996
- Subjects: Oxidation-reduction reaction , Tungsten , Hydrogen , Carbon
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4342 , http://hdl.handle.net/10962/d1005004 , Oxidation-reduction reaction , Tungsten , Hydrogen , Carbon
- Description: The reductions of WO₃ with hydrogen, with CO, and with carbon, as well as the reduction of WO₃/graphite mixtures with hydrogen, were studied using thermogravimetry, evolved gas analysis, X-ray powder diffraction, and scanning electron microscopy. The intermediate phases W₂₀O₅₈, W₁₈O₄₉ and WO₂, were observed in the reductions. The final product of the reductions with hydrogen and carbon was tungsten, and we was formed in the reduction with CO. The reaction paths in the overall processes were determined. The reactant/product gas ratio had a considerable influence on which reactions took place. The morphology of the sample was characterised at different stages of the reduction. The shape of the WO₃ particles was retained during the reduction. Particle growth was observed in the reduction with hydrogen and was attributed to the formation of WO₂(OH)₂(g). The kinetics of the reductions were investigated , and the reaction mechanisms determined. The reduction of WO₃ with CO was studied from 650 to 900°C, and occurred at a phase boundary with an activation energy of 40 kJ mol⁻¹ . The reduction of WO₂, was studied under the same conditions. The reaction also occurred at a phase boundary and had an activation energy of 62 kJ mol⁻¹. The reduction of WO₃ with carbon was studied from 935 to 1100°C and took place via CO and CO₂. Two stages were observed in the reduction . The first stage, which corresponded approximately to the formation of WO₂ had an activation energy of 66 kJ mol⁻¹ and was limited by diffusion through the porous reacting particles. The second stage was first order and had an activation energy of 40 kJ mol⁻¹. The reduction of WO₃ and WO₃ graphite mixtures with hydrogen were studied from 575 to 975 °C. The reactions were controlled by mass-transfer under the conditions investigated. The addition of carbon increased the rate of the reduction process , but did not affect the phases formed in the system. CO₂ was evolved mainly at the start, and CO mainly at the end of the process.
- Full Text:
- Date Issued: 1996
- Authors: Venables, Dean Stuart
- Date: 1996
- Subjects: Oxidation-reduction reaction , Tungsten , Hydrogen , Carbon
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4342 , http://hdl.handle.net/10962/d1005004 , Oxidation-reduction reaction , Tungsten , Hydrogen , Carbon
- Description: The reductions of WO₃ with hydrogen, with CO, and with carbon, as well as the reduction of WO₃/graphite mixtures with hydrogen, were studied using thermogravimetry, evolved gas analysis, X-ray powder diffraction, and scanning electron microscopy. The intermediate phases W₂₀O₅₈, W₁₈O₄₉ and WO₂, were observed in the reductions. The final product of the reductions with hydrogen and carbon was tungsten, and we was formed in the reduction with CO. The reaction paths in the overall processes were determined. The reactant/product gas ratio had a considerable influence on which reactions took place. The morphology of the sample was characterised at different stages of the reduction. The shape of the WO₃ particles was retained during the reduction. Particle growth was observed in the reduction with hydrogen and was attributed to the formation of WO₂(OH)₂(g). The kinetics of the reductions were investigated , and the reaction mechanisms determined. The reduction of WO₃ with CO was studied from 650 to 900°C, and occurred at a phase boundary with an activation energy of 40 kJ mol⁻¹ . The reduction of WO₂, was studied under the same conditions. The reaction also occurred at a phase boundary and had an activation energy of 62 kJ mol⁻¹. The reduction of WO₃ with carbon was studied from 935 to 1100°C and took place via CO and CO₂. Two stages were observed in the reduction . The first stage, which corresponded approximately to the formation of WO₂ had an activation energy of 66 kJ mol⁻¹ and was limited by diffusion through the porous reacting particles. The second stage was first order and had an activation energy of 40 kJ mol⁻¹. The reduction of WO₃ and WO₃ graphite mixtures with hydrogen were studied from 575 to 975 °C. The reactions were controlled by mass-transfer under the conditions investigated. The addition of carbon increased the rate of the reduction process , but did not affect the phases formed in the system. CO₂ was evolved mainly at the start, and CO mainly at the end of the process.
- Full Text:
- Date Issued: 1996
Structures and thermal behaviour of some monooxalato and dioxalato metal complexes
- Authors: Bacsa, John
- Date: 1996
- Subjects: Oxalates -- Research , Crystallography -- Research , Chemistry, Inorganic -- Research
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4351 , http://hdl.handle.net/10962/d1005016 , Oxalates -- Research , Crystallography -- Research , Chemistry, Inorganic -- Research
- Description: The crystal structure of Ba [Cu(C₂0₄)₂(H₂O)].5H₂O has been determined using single crystal X-ray diffractometry. It crystallises in the triclinic system, space group Pī , with a = 6.539(2) Å, b = 9.211(3) Å, c = 10.928(3) Å, a = 85.42(3)°, β = 79.22(3)° , γ = 80.30(3)°, V = 636.08(8)ų and Z = 2. The structure consists of [Cu(C₂0₄)₂(H₂O)]²⁻ ions weakly bridged by barium ions and water molecules. The copper(II) ions are in a tetragonally elongated square-pyramidal environment with some trigonal distortion. The two oxalate groups occupy the equatorial positions and a water molecule occupies the axial position. The barium ion is surrounded by nine oxygens: five oxygens from water molecules and four oxygens from oxalate groups. The thermal behaviour of Ba [Cu(C₂0₄)₂(H₂O)].5H₂0 in N₂ has been examined using thermogravimetry (TG) and differential scanning calorimetry (DSC). The dehydration starts at relatively low temperatures (~80°C), but continues until the onset of the decomposition (~280°C). The decomposition takes place in two major stages. The mass of the intermediate after the first stage corresponded to the formation of barium oxalate and copper metal and, after the second stage, to the formation of barium carbonate and copper metal. The enthalpy for the dehydration was found to be 311 ±30 kJ mol⁻¹. The overall enthalpy change for the decomposition of Ba[Cu(C₂0₄)₂]in N₂ was estimated from the combined area of the peaks of the DSC curve as -347 kJ mol⁻¹. The kinetics of the thermal dehydration and decomposition were studied using isothermal TG. The dehydration was strongly deceleratory and the α-time curves could be described by the three-dimensional diffusion (D3) model. The values of the activation energy and the pre-exponential factor for the dehydration were 125 ±4 kJ mol⁻¹ and (1.38 ±0.08)x10¹⁵ min⁻¹, respectively. The decomposition was complex, consisting of at least two concurrent processes. The decomposition was analysed in terms of two overlapping deceleratory processes. One process was fast and could be described by the contracting-geometry model with n = 5. The other process was slow and could also be described by the contracting-geometry model , but with n = 2. The values of Eₐ and A were 206 ±23 kJ mol⁻¹ and (2.2 ±O.5)xl0¹⁹min⁻¹, respectively, for the fast process, and 259 ±37 kJ mol⁻¹ and (6.3 ±1.8)x10²³min⁻¹, respectively, for the slow process.The crystal structure of zinc oxalate dihydrate ([Zn(C₂0₄)(H₂O)₂]n) has also been determined by X-ray diffraction methods. It crystallises in the monoclinic system, space group C2/c with a = 11.786(2) Å, b = 5.397(1)Å, c = 9.712(1) Å, B = 126.19(5)°, V = 498.58(8)ų, Z = 4 and R = 0.037 for 435 absorption-corrected independent reflections and 50 parameters. The asymmetric unit consists of half the monomeric unit [Zn(C₂0₄)(H₂O)₂). The structure consists of infinite, linear chains of zinc ions bridged by oxalate groups. The geometry of the coordination polyhedron surrounding the zinc ion is octahedral, with the oxalate oxygens occupying the equatorial positions and water molecules occupying the axial positions.
- Full Text:
- Date Issued: 1996
- Authors: Bacsa, John
- Date: 1996
- Subjects: Oxalates -- Research , Crystallography -- Research , Chemistry, Inorganic -- Research
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4351 , http://hdl.handle.net/10962/d1005016 , Oxalates -- Research , Crystallography -- Research , Chemistry, Inorganic -- Research
- Description: The crystal structure of Ba [Cu(C₂0₄)₂(H₂O)].5H₂O has been determined using single crystal X-ray diffractometry. It crystallises in the triclinic system, space group Pī , with a = 6.539(2) Å, b = 9.211(3) Å, c = 10.928(3) Å, a = 85.42(3)°, β = 79.22(3)° , γ = 80.30(3)°, V = 636.08(8)ų and Z = 2. The structure consists of [Cu(C₂0₄)₂(H₂O)]²⁻ ions weakly bridged by barium ions and water molecules. The copper(II) ions are in a tetragonally elongated square-pyramidal environment with some trigonal distortion. The two oxalate groups occupy the equatorial positions and a water molecule occupies the axial position. The barium ion is surrounded by nine oxygens: five oxygens from water molecules and four oxygens from oxalate groups. The thermal behaviour of Ba [Cu(C₂0₄)₂(H₂O)].5H₂0 in N₂ has been examined using thermogravimetry (TG) and differential scanning calorimetry (DSC). The dehydration starts at relatively low temperatures (~80°C), but continues until the onset of the decomposition (~280°C). The decomposition takes place in two major stages. The mass of the intermediate after the first stage corresponded to the formation of barium oxalate and copper metal and, after the second stage, to the formation of barium carbonate and copper metal. The enthalpy for the dehydration was found to be 311 ±30 kJ mol⁻¹. The overall enthalpy change for the decomposition of Ba[Cu(C₂0₄)₂]in N₂ was estimated from the combined area of the peaks of the DSC curve as -347 kJ mol⁻¹. The kinetics of the thermal dehydration and decomposition were studied using isothermal TG. The dehydration was strongly deceleratory and the α-time curves could be described by the three-dimensional diffusion (D3) model. The values of the activation energy and the pre-exponential factor for the dehydration were 125 ±4 kJ mol⁻¹ and (1.38 ±0.08)x10¹⁵ min⁻¹, respectively. The decomposition was complex, consisting of at least two concurrent processes. The decomposition was analysed in terms of two overlapping deceleratory processes. One process was fast and could be described by the contracting-geometry model with n = 5. The other process was slow and could also be described by the contracting-geometry model , but with n = 2. The values of Eₐ and A were 206 ±23 kJ mol⁻¹ and (2.2 ±O.5)xl0¹⁹min⁻¹, respectively, for the fast process, and 259 ±37 kJ mol⁻¹ and (6.3 ±1.8)x10²³min⁻¹, respectively, for the slow process.The crystal structure of zinc oxalate dihydrate ([Zn(C₂0₄)(H₂O)₂]n) has also been determined by X-ray diffraction methods. It crystallises in the monoclinic system, space group C2/c with a = 11.786(2) Å, b = 5.397(1)Å, c = 9.712(1) Å, B = 126.19(5)°, V = 498.58(8)ų, Z = 4 and R = 0.037 for 435 absorption-corrected independent reflections and 50 parameters. The asymmetric unit consists of half the monomeric unit [Zn(C₂0₄)(H₂O)₂). The structure consists of infinite, linear chains of zinc ions bridged by oxalate groups. The geometry of the coordination polyhedron surrounding the zinc ion is octahedral, with the oxalate oxygens occupying the equatorial positions and water molecules occupying the axial positions.
- Full Text:
- Date Issued: 1996
Synthetic and mechanistic studies of heterocyclic systems
- Authors: Deane, Philip O'Grady
- Date: 1996
- Subjects: Heterocyclic chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4379 , http://hdl.handle.net/10962/d1005044 , Heterocyclic chemistry
- Description: A series of acrylate esters and selected analogues have been reacted with pyridine-2-,pyridine-3-, and pyridine-4-carboxaldehydes in the presence of diazabicyclo[2,2,2]octane (DARCO) to afford a range of Baylis-Hillman products. The pyridine-2-carboxaldehyde-derived products have been acetylated using acetic anhydride and the kinetics of the thermal cyclisation of the acetylated compounds to indolizines was investigated using proton NMR spectroscopy. The first-order kinetics of the cyclisation has been confirmed and the influence of substituents on the first-order rate constant, kₒbs has been examined. The kinetic data has been shown to be consistent with the previously proposed mechanism in which loss of the acetate group is ratedetermining. Each of the cyclisations was also monitored at three different temperatures permitting evaluation of the activation parameters. The Baylis-Hillman products and related acetylated derivatives were treated at room temperature with sodium methylthiolate; the hydroxy precursors were observed to undergo conjugate addition with a degree of diastereocontrol but the acetylated derivatives favoured an apparent SN¹ displacement of the acetate group.
- Full Text:
- Date Issued: 1996
- Authors: Deane, Philip O'Grady
- Date: 1996
- Subjects: Heterocyclic chemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4379 , http://hdl.handle.net/10962/d1005044 , Heterocyclic chemistry
- Description: A series of acrylate esters and selected analogues have been reacted with pyridine-2-,pyridine-3-, and pyridine-4-carboxaldehydes in the presence of diazabicyclo[2,2,2]octane (DARCO) to afford a range of Baylis-Hillman products. The pyridine-2-carboxaldehyde-derived products have been acetylated using acetic anhydride and the kinetics of the thermal cyclisation of the acetylated compounds to indolizines was investigated using proton NMR spectroscopy. The first-order kinetics of the cyclisation has been confirmed and the influence of substituents on the first-order rate constant, kₒbs has been examined. The kinetic data has been shown to be consistent with the previously proposed mechanism in which loss of the acetate group is ratedetermining. Each of the cyclisations was also monitored at three different temperatures permitting evaluation of the activation parameters. The Baylis-Hillman products and related acetylated derivatives were treated at room temperature with sodium methylthiolate; the hydroxy precursors were observed to undergo conjugate addition with a degree of diastereocontrol but the acetylated derivatives favoured an apparent SN¹ displacement of the acetate group.
- Full Text:
- Date Issued: 1996
The pyrrolizidine alkaloids of Senecio chrysocoma and Senecio paniculatus
- Authors: Logie, Catherine Gwynedd
- Date: 1996
- Subjects: Senecio -- Analysis Pyrrolizidines Botanical chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4339 , http://hdl.handle.net/10962/d1005000
- Description: In order to compare the pyrrolizidine alkaloid content of two closely related species, Senecio chrysocoma and S. paniculatus, nine populations of plants distributed between the two species, were examined. Three novel pyrrolizidine alkaloids, 7ß-angelyl-l-methylene-8∝-pyrrolizidine, 7ß-angelyl-l-methylene-8∝-pyrrolizidine and 7ß-angelyl-l-methyleneSO!-pyrrolizidine-4-oxide, as well as eight known pyrrolizidine alkaloids, 7-angelylhastanecine, 9-angelylhastanecine, 7-angelylplatynecine, 9-angelylplatynecine, 9-angelylplatynecine-4-oxide, sarracine, neosarracine and retrorsine, were isolated and identified by NMR and GC-MS techniques. Traces of five tiglyl isomers, 9-tiglylplatynecine, 9-tigl ylplatynecine-4-oxide, 7ß-tiglyl-l-methylene-8∝-pyrrolizidine, sarranicine and neosarranicine, were also isolated and tentatively identified; however, these compounds could have been artefacts of the extraction and analytical procedures. While both species of plant investigated, S. chrysocoma and S. paniculatus, were found to be morphologically different, their pyrrolizidine alkaloid content was, in fact, very similar. The presence of retrorsine in S. paniculatus plant extracts, but not in those from S. chrysocoma plants, was the only major chemical difference observed. It is perhaps significant that retrorsine was the only macrocyclic pyrrolizidine to be identified. A comprehensive, computerised database of physical data for pyrrolizidine alkaloids has been compiled, which has facilitated the identification of new pyrrolizidines and the examination of trends in proton and carbon-13 NMR data for pyrrolizidine alkaloids. A stereospecific synthesis of 7ß-angelyl-l-methylene-8∝-pyrrolizidine was undertaken toconfirm the absolute stereochemistry of the product isolated from S. chrysocoma and S. paniculatus. An inseparable 5:2 mixture of 7ß-angelyl-l-methylene-8∝-pyrrolizidine and 7ß-angelyl-l,2-didehydro-l-methyl-8∝-pyrrolizidine, together with a small amount of tiglyl isomer, was finally synthesised. The application of various chiral differentiating chromatographic and spectroscopic techniques confirmed that both the natural and synthetic products had the same stereochemistry, permitting the natural alkaloid to be identified as 7ß-angelyl-methylene-8∝-pyrrol izidine
- Full Text:
- Date Issued: 1996
- Authors: Logie, Catherine Gwynedd
- Date: 1996
- Subjects: Senecio -- Analysis Pyrrolizidines Botanical chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4339 , http://hdl.handle.net/10962/d1005000
- Description: In order to compare the pyrrolizidine alkaloid content of two closely related species, Senecio chrysocoma and S. paniculatus, nine populations of plants distributed between the two species, were examined. Three novel pyrrolizidine alkaloids, 7ß-angelyl-l-methylene-8∝-pyrrolizidine, 7ß-angelyl-l-methylene-8∝-pyrrolizidine and 7ß-angelyl-l-methyleneSO!-pyrrolizidine-4-oxide, as well as eight known pyrrolizidine alkaloids, 7-angelylhastanecine, 9-angelylhastanecine, 7-angelylplatynecine, 9-angelylplatynecine, 9-angelylplatynecine-4-oxide, sarracine, neosarracine and retrorsine, were isolated and identified by NMR and GC-MS techniques. Traces of five tiglyl isomers, 9-tiglylplatynecine, 9-tigl ylplatynecine-4-oxide, 7ß-tiglyl-l-methylene-8∝-pyrrolizidine, sarranicine and neosarranicine, were also isolated and tentatively identified; however, these compounds could have been artefacts of the extraction and analytical procedures. While both species of plant investigated, S. chrysocoma and S. paniculatus, were found to be morphologically different, their pyrrolizidine alkaloid content was, in fact, very similar. The presence of retrorsine in S. paniculatus plant extracts, but not in those from S. chrysocoma plants, was the only major chemical difference observed. It is perhaps significant that retrorsine was the only macrocyclic pyrrolizidine to be identified. A comprehensive, computerised database of physical data for pyrrolizidine alkaloids has been compiled, which has facilitated the identification of new pyrrolizidines and the examination of trends in proton and carbon-13 NMR data for pyrrolizidine alkaloids. A stereospecific synthesis of 7ß-angelyl-l-methylene-8∝-pyrrolizidine was undertaken toconfirm the absolute stereochemistry of the product isolated from S. chrysocoma and S. paniculatus. An inseparable 5:2 mixture of 7ß-angelyl-l-methylene-8∝-pyrrolizidine and 7ß-angelyl-l,2-didehydro-l-methyl-8∝-pyrrolizidine, together with a small amount of tiglyl isomer, was finally synthesised. The application of various chiral differentiating chromatographic and spectroscopic techniques confirmed that both the natural and synthetic products had the same stereochemistry, permitting the natural alkaloid to be identified as 7ß-angelyl-methylene-8∝-pyrrol izidine
- Full Text:
- Date Issued: 1996
An investigation of reactions directed towards the synthesis of 2-methyl-2-(methylthio)propanal oxime
- Authors: Whittaker, Ruth Eleanor
- Date: 1995
- Subjects: Pesticides -- Synthesis , Insecticides , Aldicarb -- Synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4322 , http://hdl.handle.net/10962/d1004980 , Pesticides -- Synthesis , Insecticides , Aldicarb -- Synthesis
- Description: The processes leading to the formation of 2-methyl-2-(methylthio)propanal oxime, known industrially as aldicarb oxime, have been studied. The three stages of the synthesis, viz., chlorination, thiomethylation and oximation have been thoroughly investigated, with the aim of optimising the yield and purity of aldicarb oxime. Attention has been focused on the chlorination step, and the effects of altering various conditions have been determined; the reaction has been carried out in the absence and presence of heat, solvent and buffer, and the extent of chlorine addition has also been varied. These studies have led to some improvement in the yield for this step. Several simple and inexpensive methods for purifying contaminated batches of aldicarb oxime have also been examined. Possible aldicarb oxime contaminants, identified by GLC and GC-MS analysis, have been synthesised for use as chromatographic and spectroscopic standards, and confirmation of the presence of a number of these contaminants has been achieved. Aldehyde trimers have been found to be the primary contaminants present in aldicarb oxime and the thermal stability of these trimers, their corresponding monomers and aldicarb oxime itself has been studied using variable temperature ¹H NMR spectroscopy. Novel pyridine derivatives, with potential as aldicarb analogues, have been synthesised and characterised using spectroscopic methods.
- Full Text:
- Date Issued: 1995
- Authors: Whittaker, Ruth Eleanor
- Date: 1995
- Subjects: Pesticides -- Synthesis , Insecticides , Aldicarb -- Synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4322 , http://hdl.handle.net/10962/d1004980 , Pesticides -- Synthesis , Insecticides , Aldicarb -- Synthesis
- Description: The processes leading to the formation of 2-methyl-2-(methylthio)propanal oxime, known industrially as aldicarb oxime, have been studied. The three stages of the synthesis, viz., chlorination, thiomethylation and oximation have been thoroughly investigated, with the aim of optimising the yield and purity of aldicarb oxime. Attention has been focused on the chlorination step, and the effects of altering various conditions have been determined; the reaction has been carried out in the absence and presence of heat, solvent and buffer, and the extent of chlorine addition has also been varied. These studies have led to some improvement in the yield for this step. Several simple and inexpensive methods for purifying contaminated batches of aldicarb oxime have also been examined. Possible aldicarb oxime contaminants, identified by GLC and GC-MS analysis, have been synthesised for use as chromatographic and spectroscopic standards, and confirmation of the presence of a number of these contaminants has been achieved. Aldehyde trimers have been found to be the primary contaminants present in aldicarb oxime and the thermal stability of these trimers, their corresponding monomers and aldicarb oxime itself has been studied using variable temperature ¹H NMR spectroscopy. Novel pyridine derivatives, with potential as aldicarb analogues, have been synthesised and characterised using spectroscopic methods.
- Full Text:
- Date Issued: 1995
Reactions of iron- and zinc-fuelled pyrotechnic systems
- Authors: Tribelhorn, Michael John
- Date: 1995
- Subjects: Detonators Peroxides Chemistry, Analytic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4341 , http://hdl.handle.net/10962/d1005003
- Description: A major industrial use of pyrotechnic compositions is as delay fuses in electric detonators. Suitable delay times may be achieved through (i) choice of chemical components (ii) adjustment of composition of the system chosen and, finally, (iii) adjustment of the length of fuse used. This study forms part of a survey of binary fuel/oxidant combinations in an attempt to provide some fundamental information on the first step above: (i) choice of chemical components. The complete survey has included studies of a single fuel in combination with one of a variety of oxidants, and studies of the oxidation of one of several different fuels separately by barium peroxide and strontium peroxide. This study is part of this second approach and the fuels chosen were iron and zinc powders, mainly for chemical reasons (including the potential for use of thermomagnetometry on the iron systems), but also for possible environmental advantages. The mixed oxide products of pyrotechnic combustion could also have some scientific and/or commercial value. The techniques used included thermal analyses of mixtures and their individual components, and measurements of temperature-time profiles during combustion. Thermodynamic and kinetic information was obtained under a variety of conditions and scanning electron microscopy and X-ray diffraction and microprobe analyses provided additional information. Possible mechanisms of reactions are discussed in detail. The practical conclusions were that any potential use which the Fe/peroxide systems may have as delay compositions, with burning-rates of from 3-30 mm s⁻¹, is offset by the susceptibility of the oxidants to reaction with water and CO₂ in the atmosphere. The Zn/BaO₂ and Zn/SrO₂ systems did not burn under compaction, and combustion of uncompacted powders was erratic. Zinc liquid (and probably zinc vapour) take part in the reaction and the gaseous nature of the combustion makes zinc-fuelled pyrotechnic systems unsuitable for delay applications. All the techniques used showed the heterogeneity of the solid residues of combustion. If these residues were to be of any value, they would need further conventional treatment involving grinding of the residue, possible adjustment of compositions, and calcining to produce uniform materials.
- Full Text:
- Date Issued: 1995
- Authors: Tribelhorn, Michael John
- Date: 1995
- Subjects: Detonators Peroxides Chemistry, Analytic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4341 , http://hdl.handle.net/10962/d1005003
- Description: A major industrial use of pyrotechnic compositions is as delay fuses in electric detonators. Suitable delay times may be achieved through (i) choice of chemical components (ii) adjustment of composition of the system chosen and, finally, (iii) adjustment of the length of fuse used. This study forms part of a survey of binary fuel/oxidant combinations in an attempt to provide some fundamental information on the first step above: (i) choice of chemical components. The complete survey has included studies of a single fuel in combination with one of a variety of oxidants, and studies of the oxidation of one of several different fuels separately by barium peroxide and strontium peroxide. This study is part of this second approach and the fuels chosen were iron and zinc powders, mainly for chemical reasons (including the potential for use of thermomagnetometry on the iron systems), but also for possible environmental advantages. The mixed oxide products of pyrotechnic combustion could also have some scientific and/or commercial value. The techniques used included thermal analyses of mixtures and their individual components, and measurements of temperature-time profiles during combustion. Thermodynamic and kinetic information was obtained under a variety of conditions and scanning electron microscopy and X-ray diffraction and microprobe analyses provided additional information. Possible mechanisms of reactions are discussed in detail. The practical conclusions were that any potential use which the Fe/peroxide systems may have as delay compositions, with burning-rates of from 3-30 mm s⁻¹, is offset by the susceptibility of the oxidants to reaction with water and CO₂ in the atmosphere. The Zn/BaO₂ and Zn/SrO₂ systems did not burn under compaction, and combustion of uncompacted powders was erratic. Zinc liquid (and probably zinc vapour) take part in the reaction and the gaseous nature of the combustion makes zinc-fuelled pyrotechnic systems unsuitable for delay applications. All the techniques used showed the heterogeneity of the solid residues of combustion. If these residues were to be of any value, they would need further conventional treatment involving grinding of the residue, possible adjustment of compositions, and calcining to produce uniform materials.
- Full Text:
- Date Issued: 1995
Synthetic and spectrometric studies of benzodioxepinone derivatives
- Authors: Gelebe, Aifheli Carlson
- Date: 1995
- Subjects: Benzodiazepines -- Research Flavonoids -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4382 , http://hdl.handle.net/10962/d1005047
- Description: An extensive range of oxygen and sulphur substituted benzodiazepine analogues has been synthesised via Baeyer-Villiger and Schmidt reactions of specially prepared flavanone and N-acetyl-4-quinolone precursors. Alternative, cyclisation routes have also been used to prepare some of these compounds. Ring-opening reactions of 1,5-benzodioxepinones have been investigated and a detailed kinetic-mechanistic study of the Baeyer-Villiger reaction of flavanones has been carried out using 1 H NMR spectroscopy to explain the observed regiochemistry of oxygen insertion. The electron-impact mass spectrometric fragmentation patterns of series of 4-aryl-l ,5-benzoxathiepinones, 3-aryl-4, I-benzoxathiepinones and 3-aryl-4,1-benzoxathiepines have been studied using a combination of low-resolution, highresolution and metastable-peak analyses. The 170 NMR spectroscopic properties of various oxygenated analogues have also been studied. The binding affinities of selected benzodiazepine analogues for rat brain benzodiazepine receptors have been evaluated using a radioreceptor assay technique; at certain concentrations, some of test compounds exhibited remarkable potentiation of diazepam binding, others the ability to displace diazepam from benzodiazepine receptors. A conformational analysis of the 7-membered ring systems has been undertaken, using lH NMR spectroscopic, computer modelling and x-ray crystallographic techniques, and certain conformational preferences have been identified.
- Full Text:
- Date Issued: 1995
- Authors: Gelebe, Aifheli Carlson
- Date: 1995
- Subjects: Benzodiazepines -- Research Flavonoids -- Research
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4382 , http://hdl.handle.net/10962/d1005047
- Description: An extensive range of oxygen and sulphur substituted benzodiazepine analogues has been synthesised via Baeyer-Villiger and Schmidt reactions of specially prepared flavanone and N-acetyl-4-quinolone precursors. Alternative, cyclisation routes have also been used to prepare some of these compounds. Ring-opening reactions of 1,5-benzodioxepinones have been investigated and a detailed kinetic-mechanistic study of the Baeyer-Villiger reaction of flavanones has been carried out using 1 H NMR spectroscopy to explain the observed regiochemistry of oxygen insertion. The electron-impact mass spectrometric fragmentation patterns of series of 4-aryl-l ,5-benzoxathiepinones, 3-aryl-4, I-benzoxathiepinones and 3-aryl-4,1-benzoxathiepines have been studied using a combination of low-resolution, highresolution and metastable-peak analyses. The 170 NMR spectroscopic properties of various oxygenated analogues have also been studied. The binding affinities of selected benzodiazepine analogues for rat brain benzodiazepine receptors have been evaluated using a radioreceptor assay technique; at certain concentrations, some of test compounds exhibited remarkable potentiation of diazepam binding, others the ability to displace diazepam from benzodiazepine receptors. A conformational analysis of the 7-membered ring systems has been undertaken, using lH NMR spectroscopic, computer modelling and x-ray crystallographic techniques, and certain conformational preferences have been identified.
- Full Text:
- Date Issued: 1995
Studies in asymmetric synthesis
- Authors: Ravindran, Swarnam Shanthi
- Date: 1994
- Subjects: Asymmetric synthesis Chirality Organic compounds -- Synthesis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4352 , http://hdl.handle.net/10962/d1005017
- Description: The stereoselectivity of TiCI₄-catalysed Mukaiyama reactions of a camphor acetal-derived chiral silyl enol ether with a range of substituted aromatic aldehydes has been examined. The enantiomeric excess in each of the resulting ß-hydroxy ketones, determined by ¹H NMR spectroscopy using the lanthanide chiral shift reagent Pr(Etcf₃), ranged between 9 and 13%. The stereo-directing potential of the camphor acetal as a chiral auxiliary in the α-benzylation of carboxylate esters has been studied; the acids were chosen to illustrate substituent effects on asymmetric induction. The observed diastereoselectivity increased with increasing steric bulk of the ester group and α-benzylation of the tert-butylacetate derivative proceeded with 48% diastereoselectivity. It is proposed that the enolate adopts an endo-s-trans conformation in the transition state and preferential attack by the electrophile at the somewhat less hindered Si-face is supported by both the optical rotation data and computer modelling studies. Reductive cleavage and hydrolysis of one of the benzylated esters furnished known products from whose optical rotation the configuration of the major diastereomer was established. In order to improve the steric advantage of Si-facial attack, methods of increasing the steric bulk of the blocking group were explored. A novel 2,2-propylenedioxy hydroxycamphor acetal and its 3,3-propylenedioxy analogue were prepared. Selected carboxylate esters of these propylenedioxy acetals were subjected to α-benzylation and the 2,2-(propylenedioxy)-3-exo-tert-butylacetate derivative showed a diastereoselectivity of 57% during a-benzylation. Hydrolysis of the abenzylated phenylacetate analogue offered the known 2,3-diphenylpropanoic acid whose optical rotation indicated the preferred configuration at the new chiral centre to be (R), a result which is consistent with the proposed approach of the electrophile to the less hindered Re-face of theendo-s-trans enolate moiety and reflects an inversion of the configurational bias observed with 2-v exo-carboxylate analogues. Attempts to prepare the monocatechol acetal of the hydroxy camphor derivative although unsuccessful, led to the isolation of two novel dibornyl ethers whose structures were established by 1- and 2-D NMR spectroscopy. A study of novel applications of camphor-derived auxiliaries in the asymmetric synthesis of α-amino acids has been initiated. The several approaches tried led to the preparation of three novel dural glycine derivatives in good yield
- Full Text:
- Date Issued: 1994
- Authors: Ravindran, Swarnam Shanthi
- Date: 1994
- Subjects: Asymmetric synthesis Chirality Organic compounds -- Synthesis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4352 , http://hdl.handle.net/10962/d1005017
- Description: The stereoselectivity of TiCI₄-catalysed Mukaiyama reactions of a camphor acetal-derived chiral silyl enol ether with a range of substituted aromatic aldehydes has been examined. The enantiomeric excess in each of the resulting ß-hydroxy ketones, determined by ¹H NMR spectroscopy using the lanthanide chiral shift reagent Pr(Etcf₃), ranged between 9 and 13%. The stereo-directing potential of the camphor acetal as a chiral auxiliary in the α-benzylation of carboxylate esters has been studied; the acids were chosen to illustrate substituent effects on asymmetric induction. The observed diastereoselectivity increased with increasing steric bulk of the ester group and α-benzylation of the tert-butylacetate derivative proceeded with 48% diastereoselectivity. It is proposed that the enolate adopts an endo-s-trans conformation in the transition state and preferential attack by the electrophile at the somewhat less hindered Si-face is supported by both the optical rotation data and computer modelling studies. Reductive cleavage and hydrolysis of one of the benzylated esters furnished known products from whose optical rotation the configuration of the major diastereomer was established. In order to improve the steric advantage of Si-facial attack, methods of increasing the steric bulk of the blocking group were explored. A novel 2,2-propylenedioxy hydroxycamphor acetal and its 3,3-propylenedioxy analogue were prepared. Selected carboxylate esters of these propylenedioxy acetals were subjected to α-benzylation and the 2,2-(propylenedioxy)-3-exo-tert-butylacetate derivative showed a diastereoselectivity of 57% during a-benzylation. Hydrolysis of the abenzylated phenylacetate analogue offered the known 2,3-diphenylpropanoic acid whose optical rotation indicated the preferred configuration at the new chiral centre to be (R), a result which is consistent with the proposed approach of the electrophile to the less hindered Re-face of theendo-s-trans enolate moiety and reflects an inversion of the configurational bias observed with 2-v exo-carboxylate analogues. Attempts to prepare the monocatechol acetal of the hydroxy camphor derivative although unsuccessful, led to the isolation of two novel dibornyl ethers whose structures were established by 1- and 2-D NMR spectroscopy. A study of novel applications of camphor-derived auxiliaries in the asymmetric synthesis of α-amino acids has been initiated. The several approaches tried led to the preparation of three novel dural glycine derivatives in good yield
- Full Text:
- Date Issued: 1994
Synthesis and conformational studies of indolizines
- Authors: George, Rosemary
- Date: 1994
- Subjects: Indole alkaloids -- Research , Organic compounds -- Synthesis , Chemistry, Organic
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4367 , http://hdl.handle.net/10962/d1005032 , Indole alkaloids -- Research , Organic compounds -- Synthesis , Chemistry, Organic
- Description: The present investigation has involved a kinetic and mechanistic study of the thermal cyclization of 3-acetoxy-3-(2-pyridyl)-2-methylenepropanoate esters and related compounds to 2-substituted indolizines. Substrates for the kinetic study were prepared via the Baylis-Hillmann reaction of pyridine-2-carboxaldehydes with acrylate esters, acrylonitrile and methyl vinyl ketone. The resulting hydroxy compounds were then acetylated to afford the acetoxy derivatives, thermal cyclization of which gave the corresponding 2-substituted indolizines. The cyclization reactions was followed using 'H NMR spectroscopy and were shown to follow firstorder kinetics. The influence of the various substituents on the observed first-order rate constants has been examined and variable temperature studies have permitted evaluation of activation parameters for the formation of methyl indolizine-2-carboxylate and ethyl indolizine-2-carboxylate. An alternative route to 2-substituted indolizines via halogenated derivatives was explored and several halogenated 2-pyridyl derivatives were synthesised and their thermal cyclization to indolizines was attempted. Novel 5-methylindolizine-2-carboxamides were prepared as part of this investigation and dynamic NMR spectroscopy was used to study internal rotation about the amide N-CO bond in these compounds.
- Full Text:
- Date Issued: 1994
- Authors: George, Rosemary
- Date: 1994
- Subjects: Indole alkaloids -- Research , Organic compounds -- Synthesis , Chemistry, Organic
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4367 , http://hdl.handle.net/10962/d1005032 , Indole alkaloids -- Research , Organic compounds -- Synthesis , Chemistry, Organic
- Description: The present investigation has involved a kinetic and mechanistic study of the thermal cyclization of 3-acetoxy-3-(2-pyridyl)-2-methylenepropanoate esters and related compounds to 2-substituted indolizines. Substrates for the kinetic study were prepared via the Baylis-Hillmann reaction of pyridine-2-carboxaldehydes with acrylate esters, acrylonitrile and methyl vinyl ketone. The resulting hydroxy compounds were then acetylated to afford the acetoxy derivatives, thermal cyclization of which gave the corresponding 2-substituted indolizines. The cyclization reactions was followed using 'H NMR spectroscopy and were shown to follow firstorder kinetics. The influence of the various substituents on the observed first-order rate constants has been examined and variable temperature studies have permitted evaluation of activation parameters for the formation of methyl indolizine-2-carboxylate and ethyl indolizine-2-carboxylate. An alternative route to 2-substituted indolizines via halogenated derivatives was explored and several halogenated 2-pyridyl derivatives were synthesised and their thermal cyclization to indolizines was attempted. Novel 5-methylindolizine-2-carboxamides were prepared as part of this investigation and dynamic NMR spectroscopy was used to study internal rotation about the amide N-CO bond in these compounds.
- Full Text:
- Date Issued: 1994