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by Man Fai Shek. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (leaves 86-90). / Abstracts in English and Chinese. / Chapter I. --- ABSTRACT --- p.1 / Chapter II. --- ACKNOWLEDGEMENTS --- p.4 / Chapter III. --- CONTENT PAGE --- p.5 / Chapter IV. --- INTRODUCTION --- p.6 / Chapter A. --- CHEMISTRY OF TETRAPHENYLENES --- p.6 / Chapter B. --- CLATHRATE INCLUSION CHARACTER OF TETRAPHENYLENES --- p.8 / Chapter C. --- SYNTHESIS OF TETRAPHENYLENE AND SUBSTITUTED TETRAPHENYLENES --- p.10 / Chapter 1. --- ELECTROPHILIC AROMATIC SUBSTITUTION APPROACH --- p.10 / Chapter 2. --- SUBSTITUTED BIPHENYLENE PYROLYSIS APPROACH --- p.12 / Chapter 3. --- ARYL-HALJDE COUPLING APPROACH --- p.14 / Chapter 4. --- BIS ACETYLENE APPROACH --- p.16 / Chapter D. --- "SYNTHESIS OF TRIBENZO[α, c, e]CYCLOOCTENE" --- p.18 / Chapter E. --- "SYNTHESIS OF SUBSTITUTED TRJBENZO[α,c,e]CYCLOOCTENE" --- p.21 / Chapter F. --- THE AIM OF THE PRESENT WORK --- p.25 / Chapter V. --- RESULTS AND DISCUSSION --- p.27 / Chapter 1. --- "SYNTHETIC STUDIES OF 1,4,5,16-TETRAHYDROXYTETRAPHENYLENE FROM 1,4- DIHYDROANTHRAQUINONE" --- p.27 / Chapter 2. --- SYNTHETIC STUDIES OF 1，4，5，16-TETRAHYDROXYTETRAPHENYLENE FROM1- AMINOANTHRAQUINONE --- p.41 / Chapter 3. --- "SYNTHETIC STUDIES OF 1,4, 5，16-TETRAHYDROXYTETRAPHENYLENE FROM 1，8- DIHYDROXYANTHRAQUINONE" --- p.46 / Chapter VI. --- CONCLUSION: --- p.53 / Chapter VII. --- EXPERIMENTAL --- p.57 / Chapter VIII. --- REFERENCES --- p.86 / Chapter IX. --- APPENDIX --- p.91

Hui Chi Wai. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2003. / Includes bibliographical references (leaves 81-84). / Abstracts in English and Chinese. / Chapter I. --- Abstract --- p.ii / Chapter II. --- Acknowledgements --- p.iv / Chapter III. --- Table of contents --- p.v / Chapter IV. --- Introduction --- p.1 / Chapter A. --- Synthesis of tetraphenylene --- p.1 / Chapter B. --- Structural characteristics of tetraphenylene --- p.3 / Chapter C. --- Inclusion properties of tetraphenylene --- p.5 / Chapter D. --- Synthesis of substituted tetraphenylenes --- p.7 / Chapter 1. --- Electrophilic aromatic substitution approach --- p.7 / Chapter 2. --- Substituted biphenyl approach --- p.8 / Chapter 3. --- Substituted biphenylene approach --- p.10 / Chapter 4. --- Bis acetylene approach --- p.10 / Chapter E. --- "Synthesis of dibenzo［α ,e］cyclooctene (42) and its derivatives" --- p.14 / Chapter F. --- "Synthesis of 5,6,11,12-tetradehydrodibenzo［α ,e］cyclooctene (8) and its derivatives" --- p.16 / Chapter G. --- The aim of the present research --- p.21 / Chapter V. --- Results and discussion --- p.26 / Chapter A. --- Synthetic strategy --- p.26 / Chapter B. --- "Preparation of 1,10-dimethoxydibenzo［α ,e］cyclooctene (79)" --- p.28 / Chapter C. --- "Preparation of l，12-dimethoxytribenzo［α, c,e］cyclooctene (96)" --- p.33 / Chapter D. --- "Preparation of 1,4,5,16-tetrahydroxytetraphenylene (72) and its derivatives" --- p.44 / Chapter VI. --- Conclusion --- p.57 / Chapter VII. --- Experimental section --- p.58 / Chapter VIII. --- References --- p.81 / Chapter IX. --- Appendix --- p.85 / Chapter A. --- List of NMR Spectra --- p.86 / Chapter B. --- List of X-ray crystallographic data --- p.104

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Methyl 4-trimethylsilyl-3-dialkylaminocrotonate is synthesized by the silylation of methyl 3-dialkylaminocrotonate. It reacts with carbonyl electrophiles at its (gamma)-position. The unusual regiochemistry of this reaction is studied and rationalized. It reacts with enamines derived from acyclic ketones or cycloketones of large ring size (of 12 and 15 membered rings) to give aromatic compounds in a 3C + 3C combination and with enamines derived from cycloketones of 5-8 membered rings to give aromatic compounds in a 4C + 2C combination. The mechanism of this cycloaromatization reaction is investigated. / meta-Cyclophanes with a morpholino substituent are synthesized by the above cycloaromatization reaction. These meta-cyclophanes possess planar chirality and are successfully resolved. / A number of metacyclophanes with alkyl substituents at the intraannular position are synthesized. Depending on the ring size and the steric size of the alkyl group, some of them are also resolved. The rotation process of meta-cyclophane is studied through their temperature dependent ('1)H NMR.

The synthesis of trans-11b,11c-dimethyl-11b,11c-dihydro-7H-cyclopent [a] pyrene, 109, from trans-10b,10c-dimethyl-10b,10c-dihydropyrene, 32, was achieved in six steps in an overall yield of 29%. Deprotonation of 109 gave the first annuleno-fused cyclopentadienide, trans-11b,11c-dimethyl-11b,11c-dihydrocyclopent[a] pyrene, ion(1-), 101. Experimental and theoretical proton NMR results for the anion in the presence and absence of the counter cation were analysed. The cyclopentadienyl anion, when fused to 32, has 53% of the effective bond-fixing ability of benzene fused to the same system. In terms of benzene resonance energy units, cyclopentadienyl anion has an effective resonance energy of 0.53. Metal complexation of the cyclopent[a]dihydropyrene, 101, was investigated, and gave the first two cyclopent-fused large annulene metal complexes, (6a,7,8,9,9a- μ5]-trans-11b,11c-dimethyl-11b,11c-dihydrocyclopent[a] pyrene-pentamethylcyclopentadienylruthenium(II), 139, and (6a,7,8,9,9a- μ5) trans-11b,11c-dimethyl-11b,11c-dihydrocyclopent[a] pyrene-tricarbonylmanganese (I), 141. Experimental and theoretical 1H NMR results for the two complexes were analysed. Ruthenocene, when fused to 32, was found to be 1.38 times more bond-fixing than benzene itself. Similarly, cyclopentadienylmanganesetricarbonyl is 1.33 times more bond-fixing than benzene. In terms of benzene resonance energy units, the two complexes have effective experimental resonance energies of 1.42 and 1.36, respectively. The diamagnetic susceptibility, X, of a cyclopentadienylruthenium moiety, with the center of anisotropy located at the metal atom, was calculated as -330x10-36 m3 per molecule. The same parameter for a manganese tricarbonyl moiety, with the center of anisotropy being located at 3.2 A° down from the manganese atom, was calculated as -635x10-36 m3 per molecule. An X-ray structure determination of 32 was finally achieved some 25 years after its first synthesis. The structural data confirm the planarity and lack of bond alternation in the bridged annulene, indicating that it is aromatic. / Graduate

The preparation of 2-(3-chloro-l-naphthylmethyl)bromobenzene was achieved by the cross-condensation reaction of 3-chloro-l-naphthylmagnesium bromide and 2-bromobenzyl bromide, as well as by the reaction of this Grignard reagent with 2-bromobenzaldehyde, followed by reduction of the resulting carbinol with lithium aluminum hydride and aluminum chloride. It was found that 2-bromophenyl-1-(3-chloronaphthyl)carbinol thermally decomposed into the corresponding methylene compound and ketone. A study of the thermally induced reaction of the carbinol was made, and the products were quantitatively analyzed by means of gas chromatography. It was concluded that the anomalous products of the reaction of an aryl Grignard reagent with a benzaldehyde were actually p~duced by the thennal disproportionation of the resulting carbinols during the distillation step. The keto-acid, 2-(3-chloro-l-naphthylmethyl)- 2’-carboxybenzophenone was prepared by the inverseaddition of the Grignard reagent of 2-(3-chloro-l-naphthylmethyl)bromobenzene to phthalic anhydride. Cyclization of this keto-acid with an acetic and hydrobromic acid mixture gave 6-chloro-7-(2-carboxyphenyl)benz[a]anthracene. Methyl ester derivatives were prepared from both this acid and the precursor keto-acid. The cyclodehydration of either 2-(3-chloro-l-naphthylmethyl)-2'-carboxybenzophenone or 6-chloro-7-(2-carboxyphenyl)benz[a]anthracene with polyphosphoric acid gave 14-chlorodibenzo[hi,l]chrysen-9-one.· Treatment of this ketone with lithium aluminum hydride and aluminum chloride gave the reduction derivative, 14-chloro-9H-dibenzo[hi,l]chrysene. The unequivocal synthesis of dibenzo[hi,l]- chrysen-9-one was achieved by the dehalogenation of 14-chlorodibenzo[hi,l]chrysen-9-one with 10% palladiumcharcoal catalyst and hydrazine. The dehalogenated product was shown to be identical to the compound produced from the cyclodehydration of 7-(2-carboxyphenyl)benz[a]anthracene. The ketone, 2-(3-chloro-l-naphthylmethyl)benzophenone was prepared by the inverse-addition of the Grignard reagent of 2-(3-chloro-l-naphthylmethyl)- bromobenzene to benzoyl chloride. It was found that a small amount (16%) of 6-chloro-7-phenylbenz[a]-anthracene was formed during the distillation of the precursor ketone. The cyclodehydration of this ketone failed when various standard cyclizing media were employed, and the reason for this is discussed. Cyclization attempts with polyphosphoric acid or alumina gave dibenzo[a,l]pyrene as the only identifiable product. This unusual reaction obviously involves a rearrangement. A study was made and a mechanism for this reaction was postulated which is consistent with the experimental observations. The ketone, 2-(3-cyano-l-naphthylmethyl)benzophenone was prepared by the reaction of the corresponding chloro ketone with cuprous cyanide in N-methylpyrrolidone. 6-Cyano-7-phenylbenz[a]- anthracene was also produced in small quantity in this reaction as a consequence of the presence of the corresponding chloro compound in the ketone prior to reaction. Naphtho[3, 2, l-fg]naphthacen-9-one was prepared by the treatment of 6-cyano-7-phenylbenz[a]anthracene with a hydrobromic and acetic acid mixture at 180°, and also by the treatment of the precursor cyano ketone with polyphosphoric acid. The novel use of polyphosphoric acid in cyano group hydrolysis is discussed. Phenalo[2, 3, 4, 5-defg]naphthacene-4, 8-quinone was prepared by the treatment of 6-cyano-7-(2-carboxyphenyl)benz[a]anthracene with a hydrobromic and acetic acid mixture at 180°. An attempted procedure for the. preparation of this quinone involved the oxidation of 7-(2,6-dimethylphenyl)benz[a]anthracene to the corresponding diacid with aqueous sodium dichromate. Unfortunately this new method of oxidation failed in this case. The partial resolution of 7-(2-carboxyphenyl)-benz[a]anthracene was achieved with the use of brucine. Only one optically active isomer was obtained, and this was racemized by treatment with boiling ethanol. An empirical rule used to quantitatively determine the resistance of optically active biphenyls to racemization was applied to this acid, and the experimental observations were supported. During the course of this investigation, sixteen new compounds were prepared and were all properly characterized, except 6-cyano-7-(2-carboxyphenyl)- benz[a]anthracene, which did not give acceptable analytical data. The reason for this is discussed. Infrared and ultraviolet spectra of all new compounds were recorded. Infrared spectral observations were made which gave further support to the assigned structures of the isomeric compounds naphtho[3,2,l-fg]- naphthacen-9-one and dibenzo[hi,l]chrysen-9-one. / Doctor of Philosophy

The purpose of this investigation was to study the known methods of forming acetals and find one or several that could be used in further investigation. In connection with the reactions, the use of various catalysts was pertinent. Some of the catalysts used were hydrogen chloride, calcium chloride, ferric chloride, aromatic sulfonic acids, and other. There was no data available comparing the sulfonic acids with the inorganic salts and mineral acids. For that reason one of the subsidiary problems of this investigation was such a comparison. In order to investigate stability, several acetals were subjected to conditions intended to produce ring acetylation. These conditions are the same imposed by a Friedel Crafts reaction or a Fries rearrangement.

Chan, Chung Yin. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references (leaves 77-80). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgements --- p.iii / Abbreviations --- p.V / Abstract --- p.vi / Chapter Chapter 1 - --- Introduction --- p.1 / Chapter 1.1 --- Definition of Aromatic Bond Activation --- p.1 / Chapter 1.2 --- History of Carbon-Fluorine Bond Activation --- p.1 / Chapter 2.2.1 --- Examples of Aromatic Carbon-Fluorine Bond Activation in 1970s --- p.1 / Chapter 2.2.2 --- Examples of Aromatic Carbon-Fluorine Bond Activation in 1980s --- p.2 / Chapter 2.2.3 --- Examples of Aromatic Carbon-Fluorine Bond Activation in 1990s --- p.3 / Chapter 2.2.4 --- Examples of Aromatic Carbon-Fluorine Bond Activation in 2000s --- p.6 / Chapter 1.3 --- Difficulties and Challenges in Aromatic Bond Activation Applications of Aromatic Carbon Fluorine Bond Activation --- p.6 / Chapter 2.2.1 --- Thermodynamic Estimations --- p.7 / Chapter 2.2.2 --- Competitive Aromatic Bond Activation --- p.9 / Chapter 1.3.2.1 --- Competitive Aromatic Carbon-Hydrogen and Carbon-Halogen Bond Activation --- p.10 / Chapter 1.3.2.2 --- Competitive Aromatic Carbon-Hydrogen and Carbon-Fluorine Bond Activation --- p.15 / Chapter 1.4 --- Mechanistic Investigations of Aromatic CFA --- p.17 / Chapter 2.2.1 --- Oxidative Addition --- p.17 / Chapter 2.2.2 --- Nucleophilic Aromatic Substitution --- p.18 / Chapter 2.2.3 --- Fluorine Atom Abstraction --- p.19 / Chapter 2.2.4 --- "1,2-Addition" --- p.19 / Chapter 1.5 --- Mechanistic Investigations of Aromatic Carbon-Hydrogen Bond Activation --- p.20 / Chapter 2.2.1 --- Oxidative Addition --- p.20 / Chapter 2.2.2 --- Electrophilic Aromatic Substitution --- p.21 / Chapter 2.2.3 --- "1,2-Addition" --- p.21 / Chapter 1.6 --- Applications of Aromatic Carbon-Fluorine Bond Activation --- p.22 / Chapter 1.7 --- Applications of Aromatic Carbon-Hydrogen Bond Activation --- p.23 / Chapter 1.8 --- Structural Features of Iridium Porphyrins --- p.23 / Chapter 1.9 --- Obj ectives of the Work --- p.25 / Chapter Chapter 2 - --- Competitive Aromatic Carbon Fluorine and Carbon Hydrogen Bond Activation by Iridium(III) Porphyrins --- p.26 / Chapter 2.1 --- C-F Activation of Fluorobenzene by Rhodium(III) Porphyrins --- p.26 / Chapter 2.2 --- Preparation of Starting Materials --- p.26 / Chapter 2.2.1 --- Preparation of Tetratolylporphyrin --- p.26 / Chapter 2.2.2 --- Preparation of Iridium(III) Porphyrin Carbonyl Chloride --- p.27 / Chapter 2.3 --- Base Effect of Carbon-Fluorine Bond Activation --- p.27 / Chapter 2.4 --- Solvent Effect of Carbon-Fluorine Bond Activation --- p.30 / Chapter 2.5 --- Temperature Effect --- p.31 / Chapter 2.6 --- Concentration Effect of Carbon-Fluorine Bond Activation --- p.33 / Chapter 2.7 --- Activations of Fluorobenzenes --- p.33 / Chapter 2.8 --- Electronic Effect --- p.36 / Chapter 2.9 --- Mechanistic Studies --- p.38 / Chapter 2.9.1 --- Activation of Fluorobenzene --- p.38 / Chapter 2.9.2 --- Reaction between Ir(ttp)H and Fluorobenzene --- p.40 / Chapter 2.9.3 --- Reaction between Ir2(ttp)2 and Fluorobenzene --- p.41 / Chapter 2.9.4 --- "Reaction between Ir(ttp)""K+ and Fluorobenzene" --- p.42 / Chapter 2.9.5 --- Reaction between Ir(ttp)Me and Fluorobenzene --- p.44 / Chapter 2.10 --- Proposed Mechanism for CFA --- p.45 / Chapter 2.11 --- Proposed Mechanism for CHA --- p.47 / Chapter 2.12 --- Kinetic and Thermodynamic CFA and CHA Products --- p.47 / Chapter 2.13 --- Summary --- p.48 / Chapter Chapter 3 - --- Experimental Section --- p.49 / Reference --- p.77 / Chapter Appendix I - --- Spectra --- p.81

Lee, Man Ho. / Thesis submitted in: October 2008. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 78-83). / Abstracts in English and Chinese. / Table of Contents --- p.ii / Acknowledgements --- p.iv / Abbreviations --- p.v / Abstract --- p.vi / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Definition of Aromatic Bond Activation --- p.1 / Chapter 1.2 --- Application of Aromatic Carbon Fluorine Bond Activation --- p.1 / Chapter 1.3 --- Mechanistic Schemes Involved in Aromatic Bond Activation --- p.2 / Chapter 1.4 --- Difficulties in Aromatic Bond Activation --- p.7 / Chapter 1.5 --- Competitive Bond Activations --- p.20 / Chapter 1.6 --- Structural Features of Rhodium Porphyrins --- p.27 / Chapter 1.7 --- Objective of the Work --- p.28 / Chapter Chapter 2 --- Competitive C-F and C-H Activation of Fluorobenzenes by Rhodium(III) Porphyrins / Chapter 2.1 --- C-F Activation of Fluorobenzene by Rhodium(III) Porphyrins --- p.29 / Chapter 2.2 --- Preparation of Starting Materials --- p.29 / Chapter 2.3 --- Base Effect of CFA --- p.30 / Chapter 2.4 --- Solvent Effect of CFA --- p.32 / Chapter 2.5 --- Temperature Effect of CFA Reaction --- p.34 / Chapter 2.6 --- Activations of Fluorobenzene --- p.35 / Chapter 2.7 --- Electronic Effect of Carbon-Fluorine Bond Activations --- p.38 / Chapter 2.8 --- Preliminary Mechanistic Studies --- p.39 / Chapter 2.9 --- Proposed C-F Activation Mechanism --- p.44 / Chapter 2.10 --- Proposed C-H Activation Mechanism --- p.48 / Chapter 2.11 --- Summary --- p.51 / Chapter Chapter 3 --- Experimental Section --- p.56 / References --- p.78 / Table of Content of Appendix --- p.83 / Appendix I Crystal Data and Processing Parameters --- p.85 / Appendix II Spectra --- p.91