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Synthetic and Structural Studies of Calix[4]Pyrogallolarenes Towards Synthetic and Structural Studies of Calix[4]pyrogallolarenes Towards Biological Applications Neil Bowley A thesis submitted in partial fulfilment of the Requirements of Nottingham Trent University For the degree of Doctor of Philosophy September 2008 Acknowledgements Firstly I wish to thank my supervisor Dr. Gareth Cave for the help and advice he has provided during the three years of my Ph.D. Thanks are due to the people who I have shared a lab with over the three years of my Ph.D. The numerous project students and fellow researchers that have passed through the synthetic chemistry lab ensured my time in the lab has been interesting and sometimes entertaining! Thank you to Erasmus student Alex Massard for investigations into the solvent free preparation of calixarenes and acetals, and to M.Chem. project student Carl Rogers for synthesising bulk quantities of terpyridines. Thanks to M.Sc. students Winston Vetharoy and Kirsten Bostock under the supervision of Dr. Stéphanie. McArdle for performing cellular toxicity studies on the calixarenes. Thank you to Dr. Patrick Huddlestone, for invaluable practical advice on a variety of organic chemistry problems. Thank you to Prof. John Wallis for proofreading this thesis and many valuable contributions to my project throughout my time as a postgraduate student. Thanks to Andrew Brooks whose friendship has been a constant support throughout my time at NTU. I couldn’t have done it without you! Thank you is simply not enough to Hannah and my Parents whose unswerving support has enabled me to achieve what I could only dream of. 2 Contents Acknowledgements ................................................................................................................................ 2 Contents ................................................................................................................................................. 3 List of figures ......................................................................................................................................... 6 List of acronyms and abbreviations...................................................................................................... 10 Abstract ................................................................................................................................................ 11 Chapter 1 - Introduction ....................................................................................................................... 12 1 Supramolecular chemistry .................................................................................................. 13 2 Inter- and intramolecular interactions ................................................................................. 14 2.1 Hydrogen bonds ......................................................................................................... 15 2.2 Cation – π interactions ............................................................................................... 16 2.3 Van der Waals interactions ........................................................................................ 18 2.4 The hydrophobic effect .............................................................................................. 20 3 Host-guest chemistry .......................................................................................................... 21 3.1 Calixarenes ................................................................................................................. 24 3.1.1 Conformations of calix[4]arenes ............................................................................ 27 3.1.2 Synthesis of calix[4]resorcinarenes and calix[4]pyrogallolarenes .......................... 28 3.1.2.1 Green methods for the synthesis of calix[4]pyrogallolarene derivatives ............ 29 3.1.2.2 Green techniques for the synthesis of terpyridines ............................................. 30 3.1.3 Capsules formed by calix[4]pyrogallolarenes and calix[4]resorcinarenes ............. 31 3.1.3.1 Synthesis of capsules .......................................................................................... 33 3.1.3.2 Metal fringed capsules ....................................................................................... 34 3.1.3.3 The interior of the capsule .................................................................................. 36 3.1.3.4 Capsules in solution ........................................................................................... 37 3.1.3.5 Capsules in the gas phase ................................................................................... 39 4 Drug Delivery ..................................................................................................................... 40 4.1 Historical perspective ................................................................................................. 40 4.2 The drug development process................................................................................... 42 4.3 Why drugs fail............................................................................................................ 43 4.4 Pharmacology and Formulation ................................................................................. 45 4.5 Pro-drugs, Early Antibiotics and Nitrogen Mustards ................................................. 47 4.6 Microemulsions, Protein Carriers and Taxol ............................................................. 49 4.7 Liposomes and Doxorubicin ...................................................................................... 50 4.8 Cyclodextrins and Itraconazole .................................................................................. 52 4.9 Summary of drug delivery ......................................................................................... 54 5 Analytical Techniques ........................................................................................................ 55 5.1 Single crystal X-ray Diffraction ................................................................................. 55 5.2 Diffusion NMR spectroscopy .................................................................................... 56 Chapter 2 - Synthesis and molecular structures of C-alkyl-calix[4]arenes .......................................... 57 1 Synthesis ............................................................................................................................. 58 2 Molecular structures of C-alkyl-calix[4]arenes .................................................................. 64 3 2.1 C-Methyl-calix[4]pyrogallolarene ............................................................................. 64 2.2 C-Ethyl-calix[4]pyrogallolarene ................................................................................ 69 2.3 C-Ethyl-calix[4]resorcinarene .................................................................................... 71 2.4 C-Propyl-calix[4]pyrogallolarene .............................................................................. 73 2.5 C-Butyl-calix[4]pyrogallolarene ................................................................................ 80 2.6 C-Pentyl-calix[4]pyrogallolarene ............................................................................... 85 2.7 C-Hexyl-calix[4]pyrogallolarene ............................................................................... 87 2.8 C-Heptyl-calix[4]pyrogallolarene .............................................................................. 90 2.9 C-Octyl-calix[4]pyrogallolarene ................................................................................ 97 Chapter 3 - Host-guest chemistry of C-alkyl-calix[4]pyrogallolarenes................................................ 99 1 Introduction ...................................................................................................................... 100 2 Single crystal X-ray diffraction studies ............................................................................ 102 Chapter 4 - Green chemistry .............................................................................................................. 106 Chapter 5 - Synthesis of functionalised calixarene derivatives .......................................................... 112 1 Introduction ...................................................................................................................... 113 2 C-(Dec-10-ene)-calix[4]pyrogallolarene .......................................................................... 115 2.1 Synthetic manipulations of C-(dec-10-ene)-calix[4]pyrogallolarene (C10enePg) ... 117 3 Hydroxyl footed calix[4]arenes ........................................................................................ 119 3.1 C-(3-Propanol)-calix[4]pyrogallolarene acetone clathrate ....................................... 119 3.2 C-(3-Propanol)-calix[4]resorcinarene ...................................................................... 126 4 C-(4-nitrophenyl)-calix[4]pyrogallolarene ....................................................................... 130 Chapter 6 - Synthesis of halogenated calix[4]pyrogallolarenes ......................................................... 132 1 Synthesis ........................................................................................................................... 133 2 C-(4-Chlorobutane)-calix[4]pyrogallolarene diethyl ether clathrate ................................ 136 3 C-(4-Chlorobutane)-calix[4]pyrogallolarene propan-2-ol clathrate
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