Submitted in partial fulfillment for the Degree of Master of Applied Sciences in Biotechnology, Durban University of Technology, Durban, South Africa, 2016. / Coumarins are naturally occurring α-benzopyrone derivatives known for their pharmacological properties such as anticoagulant, antimicrobial, anticancer, antioxidant, anti-inflammatory and antiviral properties. The pharmacological, biochemical, and curative applications of coumarins depend on the substitution around the coumarin core structure. In the present study, seven halogenated coumarins CMRN1 - CMRN7 were synthesized and evaluated for mosquito larvicidal, repellancy , and insecticidal activity against Anopheles arabiensis. Furthermore, the antimicrobial properties of compounds CMRN1 - CMRN7 were evaluated by assessing the bacterial and fungicidal activities using the disc diffusion method. The anti-inflammatory properties were evaluated using the 5-lipoxygenase kit assay. The evaluation of the safe use of the compounds was determined using the Brine shrimp lethal test. The potential carcinogenic properties of the studied compounds was done using the Salmonella mutagenicity test. The anti-cancer property of the studied compounds was evaluated against UACC62 (Melanoma), MCF-7 (Breast cancer), and PBMC (Peripheral blood mononuclear) cell lines using of MTT assay. The apoptotic potential of the synthesized coumarin was evaluated against UACC62 (Melanoma) cell by assessing their morphological changes, membrane change, mitochondria membrane potential, and caspase-3 activity using the Annexin V-PI staining, JC-1, caspase-3 enzyme kits, respectively, on flow cytometer. The results were compared to a known anti-cancer drug, doxorubicin. The results showed that compounds CMRN1, CMRN2, CMRN4, CMRN5 and CMRN7 exerted 100% larval mortality within 24 h of exposure. All halogenated coumarins reversibly knocked down adult mosquitoes but did not kill them after 24 h of exposure. Furthermore, the adulticidal activity of the compounds was considered only mild to moderate. The antimicrobial activity of the synthetized coumarins CMRN1 - CMRN7 were assessed against E. coli, K. pneumoniae, S. marcescens, S. faecalis, B. cereus, B. coagulans, B. stearothermophilus, C. freundii, S. aureus and M. luteus bacteria and three yeast cultures, C. albicans, C. utilis, S. cerevisiae as well as two fungal species, A. flavus and A. niger. Compounds CMRN1 and CMRN2 showed bacterial growth inhibition for all the tested species except K. pneumonia and B. stearothermophilus. Compounds CMRN4 and CMRN7 showed moderate bacterial inhibition against B. cereus, M. luteus and S. aureus. The anti-inflammatory activity of the coumarins analogues showed that 1 mg/mL of the compounds CMRN1, CMRN2, CMRN4 and CMRN5 displayed moderate anti-inflammatory activity when compared to the positive control, 15-lapoxygenase. The cytotoxicity results of the studied synthetized coumarins displayed selective activity towards the cancer cell lines used in this study. Our studies showed that CMRN1, CMRN2, CMRN4, and CMRN5 had significant cytotoxity effect against UACC-62 (Melanoma) and MCF-7 ( Breast) cancer cells with an inhibitory concentration (IC50) which displayed significant cytotoxicity effect, in particular CMRN4 and CMRN5. These compounds CMRN1- CMRN7 showed no toxicity effect against PBMCs cell line. The mechanism of cell death, that is, necrosis or apoptosis induced by the coumarins was investigated against UACC-62 (Melanoma). We found that CMRN1, CMRN2, CMRN4, CMRN5 induced morphological changes, characteristic of apoptosis . Annexin V kit showed that CMRN1, CMRN2 and CMRN5 showed early apopotosis and late apoptosis was particularly higher for compound CMRN4. The disruption of the mitochondria membrane was noticed to be greater in CMRN1 and CMRN5 when compared to the positive control doxorubicin. Compound CMRN4 produced high levels of caspase-3 positive compared to the control. The coumarin compounds showed no mutagenicity and were also found to be non-toxic to brine shrimps. In conclusion, compounds CMRN1, CMRN2, CMRN4, CMRN5 and CMRN7 are potential larvicidal agents because they exhibited close to 100% activity within 24 h. Furthermore, the anti-cancer efficiency of compounds CMRN1, CMRN2, CMRN4, and CMRN5, is enough qualification for them to be optimized for increase anticancer potency. / M

A general straightforward synthetic approach for the enantioselective construction of medium and large ring cyclopropyl ketones via diastereoselective Simmons-Smith cyclopropanation is discussed. Medium and large 2-cycloalkenone 1,4Di-O-benzyl-L-threitol ketals undergo efficient and diastereoselective cyclopropanation when treated with an excess of the Simmons-Smith reagent. The cyclopropyl ketals are obtained in 80-94% with >23:1-8:1 diastereoselectivity. The first enantioselective synthesis of (-)-modhephene, a natural product possessing the carbocyclic (3.3.3) propellane skeleton, by the use of diastereoselective cyclopropanation methodology is described.

MSc., Faculty of Science, University of the Witwatersrand, 2011 / The 2-isopropenyl-2,3-dihydrobenzofuran moiety is found in many naturally occurring compounds including rotenone, a complex pentacyclic molecule isolated from several leguminous plants of the Derris and Lonchocarpus species. Interest in rotenone stems from the fact that it possesses significant pesticidal and piscicidal properties which have been employed for centuries. Furthermore, as it has three stereogenic centres, rotenone poses an interesting and challenging synthetic target for organic chemists. Although various syntheses of this natural compound have been reported, none of these were stereoselective. The first stereoselective total synthesis of rotenone is described in this dissertation. Initially, a model study was conducted in which the simplest of the natural rotenoids, munduserone, was synthesised. The key step in this transformation involves the use of a platinum catalysed 6-endo-hydroarylation reaction of an alkynone intermediate, thus affording munduserone in 6 steps and an overall yield of 23%. We then attended to the synthesis of the more complex rotenoid, rotenone. Rotenone was synthesised by the initial assembly of a chiral (-)-(R)-2-isopropenyl-2,3-dihydrobenzofuran-4-ol moiety, asymmetrically accessible using a stereoselective Pd π-allyl mediated cyclisation of (E)-4-(2,6-dihydroxyphenyl)-2-methylbut-2-enyl methyl carbonate. Having constructed the dihydrobenzofuran in an enantiomeric excess of 94.8%, the chromene part of rotenone could then be synthesised. To this end, the LDA mediated coupling reaction of the formylated dihydrobenzofuran and 1,2-dimethoxy-4-(prop-2-ynyloxy)benzene, gave a secondary alcohol which was subsequently oxidised to the corresponding alkynone, (-)-(R)-(6,7-dimethoxy-2H-chromen-4-yl)(4-methoxy-2-isopropenyl-2,3-dihydrobenzofuran-5-yl)methanone. A 6-endo-hydroarylation reaction was employed as a mild strategy to construct the chromene moiety, (-)-(R)-(6,7-dimethoxy-2H-chromen-4-yl)(4-methoxy-2-isopropenyl-2,3-dihydrobenzofuran-5-yl)methanone. Finally, a deprotection and a base-catalysed intramolecular oxo-Michael addition concluded the first stereoselective synthesis of rotenone in 17 steps and an overall yield of 0.02%

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Master of Science. January 1996. / Aspects of the literature of the ant venom alkaloid monomorine I and its stereoisomers were reviewed. Racemic 5-butyl-2-pyrrolidinone was synthesised in two steps from methyl acrylate and 1-nitropentane, A thionation step yielded 5-butylpyrrolidine-2-thione. The Michael addition reaction between 5-butylpyrrolidine-2-thione and ethyl crotonate proceeded with difficulty to form a separable mixture of diastereomers of 5-butyl-l-(2-ethoxycarbonyl-l-methylethyl) pyrrolidine-2-thione. [Abbreviated Abstract. Open document to view full version] / AC2017

The synthesis of alkaloids from enaminones has been used extensively in the University of the Witwatersrand’s organic chemistry laboratories. In this thesis enaminone precursors are one of the main ways of accessing lamellarin analogues. The lamellarin alkaloids are an important family of marine alkaloids, owing to their vast biological properties. A brief background to marine alkaloids and their general potential is given, followed by a review of lamellarin alkaloids, their structural and biological properties and some of the major syntheses carried out over the past few years. Two novel features form the basis of the synthetic methods described in the thesis. The first is an approach to forming the lamellarin alkaloids from enaminone precursors, which are prepared through the Eschenmoser sulphide contraction. The second method uses a novel pyrrole formation, which was initially conceptualized by Garreth L. Morgans in his PhD thesis (2008). The main target of the investigation was lamellarin G trimethyl ether. In Chapter 3, the syntheses of a range of mono-, di- and tetra-substituted phenacyl halides are discussed. The phenacyl halides were used in the preparation of various enaminone precursors. The tetrasubstituted phenacyl halide 2-bromo-1-(2-hydroxy-4,5-dimethoxyphenyl)ethanone 3.17 is required for the synthesis of our target lamellarin G trimethyl ether. The phenacyl halides are important in both the model synthesis described in Chapter 4 and the synthesis toward lamellarins in Chapter 5. Chapter 4 deals mainly with the synthesis of pyrrolizine systems. Methodology is described for the preparation of a variety of enaminones, pyrroles and tetracyclic lamellarin analogues. The closest pyrrolizine system to lamellarin G trimethyl ether, 11-(3,4-dimethoxyphenyl)-2,3-dimethoxy-9,10-dihydrochromeno[4,3-b]pyrrolizin-6(8H)-one 4.52, was the final and most complex tetracyclic model structure analogous to lamellarin G trimethyl ether. Indolizine and pyrroloazepine adaptations were also demonstrated and tetracyclic systems 10,11-dihydro-8H-chromeno[3,2-a]indolizin-12(9H)-one 4.39 and 9,10,11,12-tetrahydrochromeno[3',2':3,4]pyrrolo[1,2-a]azepin-6(8H)-one 4.40 were successfully prepared, even though the pyrrole formed in an unexpected way. Finally in Chapter 5, the methodology established in the model study was used in the attempted synthesis of lamellarin G trimethyl ether. A second method was also investigated. Thus, various N-alkylated and N-H enaminones were successfully synthesized, from which novel and unexpected pyrrole-containing products 8-(3,4-dimethoxyphenyl)-2,3-dimethoxy-5H-chromeno[3',2':3,4]pyrrolo[2,1]isoquinolin-14(6H)-one 5.28 and (3-ethoxy-8,9-dimethoxy-2-phenyl-5,6-dihydropyrrolo[2,1-a]isoquinolin-1-yl)(phenyl)methanone 5.37 were formed, even though our desired product lamellarin G trimethyl ether could not be attained from either method.

by Candy Man-Yee Chan. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1995. / Includes bibliographical references. / Acknowledgements --- p.i / Abstract --- p.ii / Contents --- p.iii / Abbreviations --- p.v / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- General aspects of group 13 organometallic chemistry --- p.1 / Chapter 1.2 --- Stability of group 13 organometallic compounds --- p.3 / Chapter 1.3 --- Group 13-15 organometallic compounds -- potential single- source precursors for semiconductors --- p.5 / Chapter 1.4 --- Objective of this work --- p.7 / Chapter 1.5 --- References --- p.9 / Chapter Chapter 2 --- Synthesis and Characterization of Group 13Metal Alkyl Halide Complexes / Chapter 2.1 --- Introduction / Chapter 2.1.1 --- General synthetic methods of organogallium and indium halide complexes --- p.10 / Chapter 2.1.2 --- Structural properties of gallium and indium organometallic halides --- p.12 / Chapter 2.1.3 --- Utilization of N-functionalized sterically hindered groups as ligands --- p.14 / Chapter 2.2 --- Results and Discussions / Chapter 2.2.1 --- Synthesis of group 13 metal alkyl complexes --- p.17 / Chapter 2.2.2 --- Characterization of group 13 metal alkyl complexes --- p.23 / Chapter 2.3 --- Experimental --- p.37 / Chapter 2.4 --- References --- p.44 / Chapter Chapter 3 --- Synthesis and Characterization of Group13- 15 Organometallic Compounds / Chapter 3.1 --- Introduction / Chapter 3.1.1 --- General routes to the formation of group 13-15 covalent bond --- p.46 / Chapter 3.1.2 --- Multiple bonding between group 13 and group 15 element --- p.48 / Chapter 3.2 --- Results and Discussions / Chapter 3.2.1 --- Synthesis of group 13-15 organometallic compounds --- p.54 / Chapter 3.2.2 --- Characterization of group 13-15 organometallic compounds --- p.57 / Chapter 3.2.3 --- Discussion on multiple bond character of group13-15 organometallic compounds --- p.72 / Chapter 3.3 --- Experimental --- p.77 / Chapter 3.4 --- References --- p.81 / Appendix I --- p.83 / Appendix II --- p.88

by Eric Kwok Wai Tam. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references. / Table of Contents --- p.i / Acknowledgement --- p.iv / Abstract --- p.v / Abbreviation --- p.vii / Part A / Enantiospecific Syntheses of Cyclohexane Oxides from (-)-Quinic Acid / Chapter 1. --- Synthetic Application of (-)-Quinic Acid --- p.1 / Chapter 1.1 --- Introduction --- p.1 / Chapter 1.2 --- Syntheses of Cyclohexane Derivatives --- p.2 / Chapter 1.2.1 --- Syntheses of Shikimic Acid (2) and its Derivatives --- p.2 / Chapter 1.2.2 --- "Syntheses of D-myo-Inositol 1,4,5-Trisphosphate (52) & its analog" --- p.15 / Chapter 1.2.3 --- Syntheses of Mycosporins --- p.17 / Chapter 1.2.4 --- Synthesis of (+)-Palitantin (76) --- p.19 / Chapter 1.2.5 --- "Synthesis of 2-Crotonyloxy-(4R,5R,6R)-4,5,6-trihydroxy- cyclohex-2-enone (COTC) (82)" --- p.20 / Chapter 1.2.6 --- Syntheses of Cyclophellitol (83) and its Diastereomers --- p.21 / Chapter 1.2.7 --- Syntheses of Pseudo-sugars and its Derivatives --- p.24 / Chapter 1.2.8 --- Syntheses of Aminocyclitol Antibiotics --- p.34 / Chapter 1.2.9 --- Syntheses of A-ring Precursor of Daunomycin --- p.36 / Chapter 1.2.10 --- "Synthesis of 19-nor-lα,25-Dihydroxyvitamin D3" --- p.38 / Chapter 1.2.11 --- Synthesis of Isoquinuclidines --- p.41 / Chapter 1.2.12 --- Synthesis of Cyclohexenyl Iodide: Taxol CD-ring Precursor --- p.44 / Chapter 1.2.13 --- Synthesis of C-20 to C-34 Segment of FK-506 --- p.46 / Chapter 1.2.14 --- Synthesis of the Hexahydrobenzofuran Subunit of Avermectins --- p.49 / Chapter 1.2.15 --- Synthesis of Bicyclic Core of Enediyne --- p.50 / Chapter 1.2.16 --- Syntheses of Two Enantiopure Derivatives of 4-Hydroxy-2-cyclohexone --- p.53 / Chapter 1.3 --- Synthesis of Homochiral Linear Molecules --- p.57 / Chapter 1.3.1 --- Syntheses of (3S)-Mevalonolactone and its Derivatives --- p.57 / Chapter 1.3.2 --- Synthesis of the Subunit in Maytansinoids --- p.58 / Chapter 1.3.3 --- Synthesis of (+)-Negamycin --- p.59 / Chapter 1.3.4 --- Syntheses of Hepoxilins B3 and its Stereoisomers --- p.61 / Chapter 1.3.5 --- Synthesis of C-21 to C-25 Fragment of FK-506 --- p.62 / Chapter 1.4 --- Synthesis of Cyclopentane Derivatives --- p.63 / Chapter 1.4.1 --- Synthesis of 11 α-Hydroxy-13-oxaprostanoic Acid --- p.65 / Chapter 1.4.2 --- Synthesis of (-)-Pentenomycin I --- p.66 / Chapter 1.4.3 --- Syntheses of Carbovir and its Derivatives --- p.66 / Chapter 1.5 --- Synthesis of Cycloheptane Derivatives --- p.68 / Chapter 1.6 --- Conclusion --- p.70 / References --- p.71 / Chapter 2. --- Introduction of Cyclohexane Oxides --- p.81 / Chapter 2.1 --- General Background --- p.81 / Chapter 2.2 --- Previous Syntheses of Cyclohexane Oxides --- p.86 / Chapter 2.2.1 --- Racemic Syntheses of Crotepoxide --- p.86 / Chapter 2.2.2 --- Racemic Syntheses of Senepoxide --- p.89 / Chapter 2.2.3 --- A Racemic Synthesis of Pipoxide --- p.92 / Chapter 2.2.4 --- Syntheses of Enantiopure Cyclohexane Oxides --- p.93 / References --- p.96 / Chapter 3. --- Retrosynthetic Analysis and Strategy --- p.99 / Chapter 3.1 --- Antithetic Analysis of Cyclohexane Oxides --- p.99 / Chapter 3.2 --- Problems Encounter in the Conversion of Diene into Cyclohexane Oxides --- p.100 / Chapter 3.3 --- Photo-oxygenation Approach to Cyclohexane Oxides --- p.102 / Chapter 3.4 --- Reasons for Choosing the Silyl Ether as Blocking Group --- p.104 / Chapter 3.5 --- Strategy for Synthesis of Diene 373 from Quinic acid --- p.105 / References --- p.106 / Chapter 4. --- Results and discussion --- p.108 / Chapter 4.1 --- Synthesis of Silyl Benzoate381 --- p.108 / Chapter 4.2 --- Synthesis of Alkene373 --- p.111 / Chapter 4.3 --- Syntheses of (+)-Crotepoxide (289)，(+)-Bosenepoxide (290) and (-)-iso-Crotepoxide (304) --- p.115 / Chapter 4.4 --- "Syntheses of the (+)-β-Senepoxide (295)，(+)-Pipoxide Acetate (365), (-) Tintanoxide (294) and (-)-Senepoxide (291)" --- p.121 / References --- p.124 / Chapter 5. --- Conclusion --- p.126 / Chapter 6. --- Experimental Section --- p.128 / References --- p.142 / Part B / Ruthenium Catalyzed cis-Dihydroxylation of Alkene / Chapter 1. --- Introduction --- p.143 / Chapter 1.1 --- Background --- p.143 / Chapter 1.2 --- General cis-Dihydroxylation Methods --- p.144 / Chapter 1.2.1 --- Potassium Permanganate (KMnO4) --- p.144 / Chapter 1.2.2 --- Osmium Tetraoxide (OsO4) --- p.146 / Chapter 1.3 --- Ruthenium Tetraoxide Oxidations --- p.148 / Chapter 1.4 --- Previous Reports of Using Ruthenium Tetraoxide (RuO4) Mediated syn-Dihydroxylation of Olefins --- p.149 / Chapter 1.4.1 --- The Snatzke and Fehlhaber Work --- p.149 / Chapter 1.4.2 --- The Sharpless and Akashi Work --- p.150 / Chapter 1.4.3 --- The Sica and Co-workers Work --- p.150 / References --- p.152 / Chapter 2. --- Ruthenium-Catalyzed cis-Dihydroxylation of Alkenes --- p.155 / Chapter 2.1 --- """Flash"" Dihydroxylation" --- p.155 / Chapter 2.2 --- "Stereochemical Outcome of ""Flash"" Dihydroxylation" --- p.155 / References --- p.157 / Chapter 3. --- Results and Discussion --- p.158 / Chapter 3.1 --- "Scope and Limitations of ""Flash"" Dihydroxylation" --- p.158 / Chapter 3.2 --- "Study of the Diastereoselectivity of ""Flash"" Dihydroxylation" --- p.168 / Chapter 3.3 --- "Study of Co-oxidants for ""Flash"" Dihydroxylation" --- p.170 / Chapter 3.4 --- "Solvent Effect for ""Flash"" Dihydroxylation" --- p.171 / Chapter 3.5 --- "Synthetic Application of ""Flash"" Dihydroxylation" --- p.173 / References --- p.175 / Chapter 4. --- Conclusion --- p.176 / Chapter 5. --- Experimental Section --- p.177 / References --- p.185 / Appendix --- p.186

by Xiang Zhou. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references. / Acknowledgment --- p.i / Abstract --- p.ii / Abbreviations --- p.iii / Table of Contents --- p.iv-v / Chapter Chapter I --- Synthesis of β-substituted porphyrins --- p.1 / Chapter I-1 --- Introduction --- p.1 / Chapter I-1-1 --- Activation of alkanes: the biomimetic approach --- p.2 / Chapter I-1-2 --- Electronic effects in β-substituted porphyrins --- p.5 / Chapter I-1-3 --- Synthetic approach to β-substituted porphyrins --- p.7 / Chapter I-2 --- Results and discussions --- p.14 / Chapter I-2-1 --- Bromination of porphyrins at β-positions --- p.14 / Chapter I-2-2 --- Synthesis of boronic acids --- p.17 / Chapter I-2-3 --- Synthesis of β-substituted porphyrins --- p.18 / Chapter I-2-4 --- Uv spectra --- p.25 / Chapter I-2-5 --- "Crystal structures of H2TPP(Ph)4, H2TPP(Me)4， H2TPP(Tol)8 and H2TMP(Ph)8" --- p.26 / Chapter I-3 --- Conclusion --- p.43 / Chapter I-4 --- Experimental section --- p.44 / Chapter I-5 --- References --- p.58 / Chapter Chapter II --- Synthesis and Properties of Diporphyrins --- p.63 / Chapter II-1 --- Introduction --- p.63 / Chapter II-1-1 --- Linear dimers --- p.64 / Chapter II-1-2 --- Cofacial porphyrins (or strati-bisporphyrins) --- p.68 / Chapter II-1-3 --- Synthetic approach --- p.71 / Chapter II-2 --- Results and discussions --- p.73 / Chapter II-2-1 --- Synthetic strategy --- p.73 / Chapter II-2-2 --- Synthesis of diporphyrins via condensation and Suzuki cross- coupling --- p.75 / Chapter II-2-3 --- Synthesis of diporphyrins via Suzuki cross-coupling and condensation --- p.75 / Chapter II-2-4 --- Metalation of diporphyrins --- p.78 / Chapter II-2-5 --- Spectroscopy --- p.81 / Chapter II-3 --- Conclusion --- p.89 / Chapter II-4 --- Experimental section --- p.90 / Chapter II-5 --- Reference --- p.100 / Chapter Chapter III --- Novel Rhodium Porphyrin Complexes: Intermolecular Activation of Arene Carbon-Hydrogen Bond and Formation of a Nitrile-Bridged Coordination Polymer --- p.104 / Chapter III-l --- Introduction --- p.104 / Chapter III-1-1 --- Activation of C-H bonds --- p.104 / Chapter III-1-2 --- Activation of C-H bond by rhodium porphyrin complexs --- p.106 / Chapter III-2 --- Results and discussions --- p.108 / Chapter III-2-1 --- Synthesis of rhodium porphyrin complexes --- p.108 / Chapter III-2-2 --- Proton NMR --- p.112 / Chapter III-2-3 --- UV and binding studies of rhodium porphyrin complexes --- p.115 / Chapter III-2-4 --- IR spectra --- p.117 / Chapter III-2-5 --- Crystal structures of rhodium porphyrin complexes --- p.118 / Chapter III-3 --- Conclusion --- p.148 / Chapter III-4 --- Experimental section --- p.149 / Chapter III-5 --- References --- p.154 / Appendix --- p.157 / NMR Spectra --- p.159

by Chi-Hang Lee. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (leaves 71-80). / Abstracts in English and Chinese. / ABSTRACT --- p.i / ACKNOWLEDGMENT --- p.iv / TABLE OF CONTENTS --- p.v / LIST OF SCHEMES --- p.vii / LIST OF FIGURES --- p.viii / LIST OF TABLES --- p.x / ABBREVIATIONS --- p.xi / Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Discovery of Phthalocyanines --- p.1 / Chapter 1.2 --- Synthesis of Phthalocyanines --- p.4 / Chapter 1.2.1 --- Metal-Free Phthalocyanines --- p.4 / Chapter 1.2.2 --- Metallophthalocyanines (MPcs) --- p.5 / Chapter 1.2.3 --- Sandwich Complexes (MPc2) --- p.7 / Chapter 1.2.4 --- Tetra-Substituted Phthalocyanines --- p.8 / Chapter 1.2.5 --- "2,3,9,10,16,17,23,24-Octa-substituted Phthalocyanines" --- p.11 / Chapter 1.2.6 --- "1,4,8,11,15,18,22,25-Octa-substituted Phthalocyanines" --- p.12 / Chapter 1.3 --- Mechanism for Phthalocyanine Formation --- p.14 / Chapter 1.4 --- Purification of Phthalocyanines --- p.16 / Chapter 1.5 --- Characteristics of Phthalocyanines --- p.17 / Chapter 1.5.1 --- Electronic Structure --- p.17 / Chapter 1.5.2 --- Absorption Spectra --- p.17 / Chapter 1.5.3 --- X-Ray Diffraction Studies --- p.19 / Chapter 1.6 --- Applications of Phthalocyanines --- p.20 / Chapter 1.6.1 --- Colorants --- p.20 / Chapter 1.6.2 --- Photodynamic Therapy --- p.21 / Chapter 1.6.3 --- Catalysis --- p.22 / Chapter 2 --- Results and Discussion --- p.23 / Chapter 2.1 --- "Preparation, Spectroscopic Properties, and Structure of Phthalocyanines Substituted with Four 2,4-Dimethyl-3- pentyloxy Moieties" --- p.23 / Chapter 2.1.1 --- Synthetic Studies --- p.24 / Chapter 2.1.2 --- UV-Vis Spectra --- p.28 / Chapter 2.1.2.1 --- Effects of Metal Center --- p.28 / Chapter 2.1.2.2 --- Effects of Substituents --- p.30 / Chapter 2.1.2.3 --- Effects of Concentration --- p.30 / Chapter 2.1.2.4 --- Absorption Spectra of MnClPc(OC7H15)4 (10) --- p.34 / Chapter 2.1.3 --- 1H NMR Spectra --- p.35 / Chapter 2.1.4 --- Structural Studies --- p.38 / Chapter 2.1.4.1 --- Molecular Structures of ZnPc(OC7H15)4 (3) and CoPC(OC7H15)4 (5) --- p.39 / Chapter 2.1.4.2 --- Molecular Structure of MnClPc(OC7H15)4 (10) --- p.41 / Chapter 2.2 --- Formation and Crystal Structures of Novel Inclusion Complexes of Phthalocyanines and Oxalic Acid --- p.43 / Chapter 2.2.1 --- 1:1Complex with Metal-free Phthalocyanine (8) --- p.43 / Chapter 2.2.2 --- 1:1Complexes with Palladium Phthalocyanine (4) --- p.49 / Chapter 2.2.3 --- Conclusion --- p.51 / Chapter 2.3 --- Cerium Promoted Formation of Metal-Free Phthalocyanines --- p.52 / Chapter 2.3.1 --- Introduction --- p.52 / Chapter 2.3.2 --- Preparation of Metal-free Phthalocyanines --- p.52 / Chapter 2.3.3 --- Conclusion --- p.58 / Chapter 3 --- Experimental --- p.59 / Chapter 3.1 --- General --- p.59 / Chapter 3.2 --- "Synthesis of 3-(2,4-dimethyl-3-pentyloxy)phthalonitrile (2)" --- p.60 / Chapter 3.3 --- "Synthesis of ZnPc(OC7H,5)4 (3 and 6)" --- p.61 / Chapter 3.4 --- Synthesis of PdPc(OC7H15)4 (4 and 7) --- p.62 / Chapter 3.5 --- Synthesis of CoPc(OC7H15)4 (5) --- p.64 / Chapter 3.6 --- Synthesis of H2Pc(OC7H15)4 (8) --- p.64 / Chapter 3.7 --- Synthesis of MnClPc(OC7H15)4 (10) --- p.66 / Chapter 3.8 --- General Procedure for the Cerium-Promoted Cyclization of Phthalonitriles --- p.67 / Chapter 3.9 --- X-ray Crystallographic Analyses --- p.69 / Chapter 4 --- REFERENCES --- p.71 / APPENDIX A lH and13 C̐ưث1H} NMR spectra / APPENDIX B X-ray Crystallographic Data

Leung, Chi Yin. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references (leaves 81-89). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts also in Chinese.