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Synthesis of Polyrotaxanes Containing Cucurbituril

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Synthesis of Polyrotaxanes Containing Cucurbituril SYNTHESIS OF POLYROTAXANES CONTAINING CUCURBITURIL By Donus Tuncel A thesis submitted for the degree of Doctor of Philosophy at Imperial College of Science, Technology and Medicine January 2000 Statement of Copyright The copyright of this thesis rests solely with the author. No quotation from it should be published without the written consent of the author and information derived from it should be acknowledged. Declaration The work described in this thesis was carried out in the Department of Chemistry at the University of Cambridge between October 1996 and January 97, and in the Department of Chemistry at Imperial College of Science, Technology and Medicine between January 1997 and September 1999, the entire body of work is my own unless to the contrary and has not been submitted previously for a degree at this or any other University. Dedicated to Mehmet and Isil. Ill Acknowledgements Firstly I must thank my superviser, Dr Joachim Steinke for his constant help, enthusiasm and encouragement throughout the course of this project and also for giving me the opportunity working on this fascinating project. I am particularly grateful to Dr Welham (University of London ULIRS Service) for MALDI-TOF spectroscopy and RAPRA for GPC analysis. Prof David Williams and Dr Andrew White (Imperial College) for X-ray crystallography. I would like to thank all of the technical staff of Chemistry Department of Imperial College for their friendly assistance, in particular R.Sheppard for NMR, J.Barton for MS. Many thanks must also go to the Steinke Group-past and present members- especially Peter Cormack (Melville Lab, University of Cambridge), Laurence (also many thanks for DSC), Yi Ying, Kwok Tung, Clare, Alberto, Anne-Laure, Cam, Mohammed, Gabriel, Gregor, Finally, I must thank the EPSRC for their financial support. IV Thesis Abstract Synthesis of Polyrotaxanes Containing Cucurbituril The abiUty of cucurbituril to catalyse 1,3-dipolar cycloadditions between alkyne and azido-substituted moieties has been extended to the synthesis of structurally well-defined polymers. We describe the first example of a polyrotaxane which contains a predictable number of threaded macrocycles per repeat unit due to the synthetic strategy of catalytic self-threading which has been employed. In order to adopt the catalysis of cucurbituril to the synthesis of polymers a variety of aromatic and aliphatic dialkyne and diazido monomers were synthesised. Polymerisation was achieved only with the aromatic monomers. The resulting polymers were characterised using standard techniques and their molecular weights were determined by NMR, GPC and mass spectrometry (FAB, ES, MALDI-TOF). Investigations into the polymerisation mechanism have produced a hypothesis, which explains the observed reactivity pattern. In the course of the mechanistic investigation a set of novel [2], [3] and [4] rotaxanes and pseudorotaxanes were also synthesised. The elusive aliphatic cucurbituril- containing polyrotaxanes were synthesised through post-threading of reduced nylons, in particular nylon 6, with cucurbituril. A series of polyrotaxanes with varying degrees of threading were synthesised and the effect of the degree of threading on solution and solid phase behaviour studied. Finally, a number of preliminary experiments were conducted to extend the architectural diversity of cucurbituril-containing polymers to hyperbranched and dendritic as well as sidechain polyrotaxanes via the catalytically self-threading concept. These syntheses require further work to establish a detailed picture of the molecular structures obtained. Abbreviations NMR Nuclear Magnetic Resonance 6 Chemical Shift ppm parts per million Mn Number average molecular weight GPC Gel Permeation Chromatography QQ Cucurbituril DSC Differential Scanning Calorimetry DP Degree of Polymerisation DSS 3-(TrimethyI silyl)-l-propanesulfonic acid, sodium salt IR Infra red Mw Weight average molecular weight PDI Polydispersity Index Tg Glass transition temperature lAA 2-t-Indoleacrylic acid MALDI-TOF Matrix Assisted Laser Desorption lonisation Time of Flight ACVA 4,4'-Azobis(4-cyanovaleric acid) Note: The counter ion chloride was omitted in some of the figures when ammonium ions were used. VI Table of Contents I. Introduction 1 1.1. Polyrotaxanes 2 1.1.1. Introduction 2 1.1.2. Definitions 3 1.1.3. Synthesis of Rotaxanes/Polyrotaxanes 4 1.1.4. A Brief Overview of the Synthesis of Rotaxanes 5 1.1.5. Classes of Rotaxanes/Polyrotaxanes 10 1.1.6. Main Chain Rotaxanes 11 1.1.6.1. Examples of Mainchain Polyrotaxanes 11 1.1.7. Side Chain Rotaxanes 25 1.1.7.1. Examples of Sidechain Polyrotaxanes 26 1.1.8. Branched/Dendritic Polyrotaxanes 30 1.1.9. Examples of Physical Properties of Polyrotaxanes 32 1.2. Cucurbituril 35 1.3. References 49 II. Results and Discussion 55 ILL Synthesis of Monomers 56 II.l.l .Introduction 56 11.1.2.Synthesis of Cucurbituril 1 58 11.1.3.Monomers Used in the Synthesis of Linear Polypseudorotaxanes 61 Vll 11.1.3.1. Synthesis of N', N®-bis(2-azidoethyl)-l,6-hexanediamine dihydrochloride 9 62 11.1.3.2. Synthesis of N', N^-bis(2-azidoethyl)-l,6-hexanedianiine dihydrochloride 12 63 II. 1.4. Monomers Used in the Synthesis of Linear Polyrotaxanes 65 II.1.4.1. Attempted Synthesis ofN-({10-[2-propynylamino)methyl]-9- anthryl}methylene)-2-propyn-l-amine 31 65 II. 1.4.2. Attempted Reduction of 5-^ert-butyl-JV'^^-di(2-propyny])isophthalamide 32b 67 II. 1.4.3. N- {2,4,6-trimethyl-3-[(2-propynylamino)methyl}benzyl}-2-propyn-1 - amine dihydrochloride 18 68 II. 1.4.4. Synthesis of N-(2-azidoethyl)-N-(3-{{(2-azidoethyl)amino]methyl}- 2,4,6-trimethylbenzyl)amine dihydrochloride 22 70 II. 1.5. Monomer Used in the Synthesis of Sidechain Polyrotaxanes 72 II.1.5.1. Synthesis of N-(3-butynyl)-N-(4-vinylbenzyl)amine hydrochloride salt 29 72 II.1.6. Monomers Used in the Synthesis of Hyperbranched Polyrotaxanes 73 II. 1.6.1. Syntesis ofNN-{2,4,6-trimethyl-3,5-bis[(2- propynyIamino)methyl]benzyl}-2-propyn-l-amine trihydrochloride 24 73 11.2.Synthesis of [n]Rotaxanes and Pseudo[n]rotaxanes 75 II.2.1. Introduction 75 II.2.2.Synthesis of [nJRotaxanes 77 II.2.2.1.Synthesis of [2]Rotaxane 33 77 Vlll 11.2.2.2. Synthesis of [3]Rotaxane 34 80 11.2.2.3. Synthesis of [3]Rotaxane 35 82 n.2.2.4. Synthesis of [4]Rotaxane 36 84 11.2.3. Synthesis of Pseudo[n]Rotaxanes 86 11.2.3.1. Synthesis of Senii[2]Rotaxane 37 86 11.2.3.2. Synthesis of Pseudo[2]Rotaxane 40 89 11.2.3.3. Synthesis of Pseudo[3]Rotaxane 42 91 11.2.3.4. Synthesis of Pseudo[4]Rotaxane 44 92 11.2.4. Dethreading of Pseudo[n]Rotaxanes 95 11.2.4.1. Synthesis of A^-{2-[l-(aminomethyl)-l/f-l,2,3-triazol-4-yl]ethyl}-A/^-(tert- butyl)amine 38 95 11.2.4.2. Synthesis of [l-(2-aminoethyl)-l//-l,2,3-triazol-4-yl]methylamine 41...97 11.2.4.3. Synthesis ofN-{[l-(2-aminoethyl)-l/f-l,2,3-triazol-4-yl]methyl}-N-{3- [({[l-(2-aminoethyl)-l//-l,2,3-triazol-4-yl}methyl}amino)methyl]-2,4,6- trimethylbenzyl} amine 43 97 11.2.4.4. Synthesis ofN-{[l-(2-aminoethyl)-177-l,2,3-triazol-4-yl]methyl}-N-{3,5- bis[({[l-(2-aminoethyl)-l/f-l,2,3-triazol-4-yl}methyl}amino)methyl]-2,4,6- trimethylbenzyl} amine 45 99 II.3. Synthesis of Linear, Catalytically Self-Threading Polypseudorotaxanes and Polyrotaxanes 101 11.3.1. Introduction 101 11.3.2. Attempted Synthesis of Linear, Catalytically Self-Threading Polypseudorotaxanes 52 101 IX 11.3.2.1. Summary 109 II.3.3. Syntesis of Linear, Catalytically Self-Threading Polyrotaxanes 110 IL3.3.2. Determination of Mn by 'H-NMR 114 IL3.3.3. Other Characterisation Techniques 116 n.3.3.3.1. Matrix Assisted Laser Desorption lonisation Time of Fhght Mass Spectrometry (MALDI-TOF) 116 n.3.3.3.2. Gel Permation Chromatography (GPC) 118 11.3.3.4. Conclusion 124 11.4. Synthesis of Catalytically Self-Threading Hyperbranced and Dendritic Polyrotaxanes 127 IL4.1. Attempted Synthesis of Catalytically Self-Threading Dendritic Polyrotaxanes 127 IL4.2. Conclusions 133 11.4.3.Synthesis of Catalytically Self-Threading Hyperbranched Polyrotaxanes 133 11.5. Attempted Synthesis of Side Chain Polyrotaxanes 139 11.5.1. Attempted Polymerisation of n-(tert-butyl)-N-[2-(4-{[(4-vinyl benzyl)amino]methyl}-lH-l,2,3-triazole-l-yl)ethyl]amine hydrochloride salt-semi[2]rotaxane 139 11.5.1.2. Attempted Polymerisation of Semi[2]rotaxane 64 141 IL5.2. Synthesis of Polyrotaxanes via a Polymer-analogous Reaction 144 II.5.3. Conclusions 150 11.6. Synthesis of Linear Polypseudorotaxanes by Post-ThreadingMethod 151 11.6.1. Synthesis of Poly(iminohexamethylene) 76 151 11.6.2. Synthesis ofPolypseudorotaxanes 77 152 11.6.2.1. Evaluation of ^H-NMR Data, Calculation of the Degree of Threading and the Determination of Molecular weights (Mn) 155 11.6.2.2. Work-up of 77 155 11.6.2.3. Differential Scanning Calorimetry (DSC) 156 11.6.3. Conclusions 156 11.6.4. References III. Experimental 161 References 219 XI I. INTRODUCTION I.l. Polyrotaxanes 1.1.1. Introduction The total volume of synthetic polymers consumed is overtaking that of traditional materials such as iron and steel. There are reasonable economic reasons for the increasing use of synthetic polymers. They weigh less and are generally more corrosion resistant than metals. Like metals they are blended (alloyed) to improve their properties. With increasing cost of energy, it is of particular importance that they can be manufactured and processed with lower energy input than either metals or glass.^ Consequently, the increasing demand for synthetic polymers has directed research to produce more versatile polymeric structures covering a wider range of properties with new polymeric architectures.^ Seeking architectural novel polymers^ led polymer chemist to synthesise numerous hyperbranched"^ and dendritic polymers.^ Finally even polycatananes and polyrotaxanes^"^ are starting to get attention from the polymer chemist as potentially interesting new materials.
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