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Synthesis and Characterization of Polyurethane Dendrimers and Subsequent Click Reactions

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Synthesis and Characterization of Polyurethane Dendrimers and Subsequent Click Reactions MIAMI UNIVERSITY The Graduate School Certificate for Approving the Dissertation We hereby approve the Dissertation of Fahad M. Alminderej Candidate for the Degree Doctor of Philosophy ______________________________________ Richard T. Taylor, Director ______________________________________ C. Scott Hartley, Reader ______________________________________ Benjamin W. Gung, Reader ______________________________________ Neil D. Danielson, Reader ______________________________________ Fazeel Khan, Graduate School Representative ABSTRACT SYNTHESIS AND CHARACTERIZATION OF POLYURETHANE DENDRIMERS AND SUBSEQUENT CLICK REACTIONS by Fahad M. Alminderej The synthesis of polyurethane dendrimers was achieved with a divergent approach, using different cores and building different generations. Diethylene glycol, triethylene glycol, 2-butyne-1,4-diol and 2-butene-1,4-diol were used as cores to synthesize polyurethane dendrimers by using diphenyl phosphoryl azide. The convergent strategy and the selectivity of the reactions of alkene alcohols on the periphery have been applied to the synthesis of a polyurethane wedges. The first and second generation polyurethane wedges with allyl or pentene peripheries were prepared. The thiol functional group was reacted with an alkene to create first and second generation polyurethane wedges with thiol-ene click periphery. The polyurethane wedges were used to synthesize polyurethane dendrimers. The synthesis of the first and second generation polyurethane wedges with peripheral alkyne groups was achieved with a convergent approach. The first and second generation polyurethane wedges with a pentyne periphery were prepared. The first generation polyurethane with pentyne periphery was useful for click reaction with boronic acid, 4-azidobenzoic acid, and 3-azido-7-hydroxycoumarin. The first and second generation polyurethane wedges with pentyne or triazoles peripheries were used to prepare several kinds of dendrimers. SYNTHESIS AND CHARACTERIZATION OF POLYURETHANE DENDRIMERS AND SUBSEQUENT CLICK REACTIONS A DISSERTATION Presented to the Faculty of Miami University in partial fulfillment of the requirements for the degree of Doctor of Philosophy Department of Chemistry & Biochemistry by Fahad M. Alminderej The Graduate School Miami University Oxford, Ohio 2016 Dissertation Director: Richard T. Taylor © Fahad M. Alminderej 2016 TABLE OF CONTENTS CHAPTER PAGE List of tables viii List of figures ix List of abbreviations & acronyms xii Acknowledgement xiii I Literature Review of Dendrimers 1 1-1 Theoretical 1 1-2 Synthesis of Dendrimers 2 1-3 Dendrimers review 5 1.4 Polyurethane review 7 1-4-1 Introduction 7 1-4-2 Linear polyurethanes 8 1-4-3 Polyurethane dendrimers and hyperbranched polymers 10 1-4-4 Application of polyurethane dendrimers 16 1-5 Our group research 17 1-6 References 20 II Synthesis of polyurethane dendrimer via divergent approach 23 2-1 Introduction 23 2-1-1 Specific aims 23 2-1-2 Synthetic strategies 23 iii 2-2 Divergent syntheses of polyurethane dendrimers 24 2-2-1 Synthesis of branching monomer 24 2-2-2 Synthesis of polyurethane dendrimer 25 2-2-2-1 Synthesis of diethylene glycol (DEG) polyurethane dendrimer 27 2-2-2-2 Synthesis of triethylene glycol (TEG) polyurethane dendrimer 28 2-2-2-3 Synthesis of 1,4-Bis(2-hydroxyisopropyl)benzene polyurethane dendrimer 29 2-2-2-4 Synthesis of 2-butyne-1,4-diol polyurethane dendrimer 30 2-2-2-5 Synthesis of 2-butene-1,4-diol polyurethane dendrimer 31 2-3 Core effect 32 2-4 Solvent effect 33 2-5 Conclusions 34 2-6 Experimental section 35 2-6-1 Synthesis of branching monomer 35 2-6-2 Synthesis of polyurethane dendrimers 37 2-7 References 44 III Synthesis of alkene polyurethane dendrimer via convergent approach 45 3-1 Introduction 45 3-1-1 Specific aims 46 3-1-2 Synthetic strategies 46 3-2 Synthesis of polyurethane wedge with ally periphery 47 3-2-1 Initial model A 47 iv 3-2-2 Initial model B 49 3-2-3 Synthesis of branching monomer 51 3-2-4 Synthesis of polyurethane wedge with allyl periphery 52 3-2-5 Synthesis of polyurethane dendrimer with allyl periphery 55 3-3 Conclusions 56 3-4 Experimental section 57 3-5 Synthesis of polyurethane with pentene periphery 63 3-5-1 Synthesis of polyurethane wedge with pentene periphery 63 3-5-2 Thiol-ene “click” chemistry of polyurethane wedge with pentene periphery65 3-5-3 Synthesis of polyurethane dendrimers 67 3-5-3-1 Synthesis of polyurethane dendrimers from 4,4'-MDI and 4,4'- biphenyldicarboxylic acid. 68 3-5-3-2 Synthesis of polyurethane dendrimers from trimesic acid 69 3-5-3-3 Synthesis of polyurethane dendrimers from sebacic acid as ester functional group core 70 3-5-3-4 Synthesis of polyurethane dendrimers from porphyrin as ester functional group core 72 3-5-4 Conclusions 74 3-5-5 Experimental section 74 3-6 References 79 IV Synthesis of alkyne polyurethane dendrimer via convergent approach and click chemistry reactions 80 4-1 Introduction 80 v 4-1-1 Specific aims 81 4-1-2 Synthetic strategies 81 4-2 Synthesis of polyurethane with propargyl periphery 83 4-2-1 Synthesis of polyurethane wedge with propargyl periphery 83 4-2-2 Synthesis of polyurethane dendrimers 86 4-3 Conclusions 87 4-4 Experimental section 88 4-5 Synthesis of polyurethane with pentyne periphery 90 4-5-1 Synthesis of polyurethane wedge with pentyne periphery 90 4-5-2 Synthesis of polyurethane wedge with a subsequent click reaction periphery92 4-5-2-1 First generation wedge click reaction with 4-azidobenzoic acid 92 4-5-2-2 First and second generation wedge click reaction with phenyl boronic acid93 4-5-2-3 First generation wedge click reaction with 3-azido-7-hydroxycoumarin 95 4-5-3 Synthesis of polyurethane dendrimers 96 4-5-3-1Synthesis of polyurethane dendrimers from trimesic core with pentyne periphery 97 4-5-3-2 Synthesis of polyurethane dendrimers from trimesic core with phenyl-triazoles periphery 99 4-5-3-3 Synthesis of polyurethane dendrimers from sebacic core with pentyne periphery 100 4-5-3-4 Synthesis of polyurethane dendrimers from sebacic core as ester functional group core 100 vi 4-5-3-5 Synthesis of polyurethane dendrimers from trimesic as ester functional group core 102 3-5-3-6 Synthesis of polyurethane dendrimers from porphyrin as ester functional group core 104 4-6 Conclusions 106 4-7 Experimental section 106 Conclusion and future research 114 4-8 References 115 vii LIST OF TABLES TABLE PAGE 1. The cores 27 viii LIST OF FIGURES FIGURE PAGE 1. Model of dendrimer and hyperbranched polymer 2 2. Schematic of the divergent path 3 3. Schematic of the convergent path 4 4. Polyamine dendrimer synthesis by divergent path 5 5. Poly (ether amide) dendrimers by a divergent path 6 6. Poly (benzyl ether) dendrimers 7 7. Linear polyurethanes synthesized 8 8. Linear polyurethanes synthesized 8 9. Linear polyurethanes synthesized 9 10. Linear polyurethanes synthesized by DPPA 9 11. Polyurethanes synthesized by polymer-supported DPPA 10 12. Polyurethanes synthesized by CDI 10 13. Polyurethane dendrimers by Spindler and Frechet 11 14. Polyurethane dendrimers by Bruchmann et al 12 15. Polyurethane dendrimers by Taylor et al 13 16. Synthesis of alternating urethane and urea aliphatic dendrimers 14 17. Polyurethane dendrimer by Alison Stoddart et al. 15 18. Polyurethane dendrimer by Moeller et al. 16 19. Aliphatic polyurethane dendrimer for drug delivery system 17 20. Porphyrin-cored third generation polyurethane dendrimer 18 21. Divergent synthesis of a polyurethane dendrimer 19 22. Divergent path synthesis strategies 24 23. Synthesis of branching monomer 25 24. Synthesis of isocyanate intermediate 26 25. Diethylene glycol polyurethane dendrimer synthesis 28 26. Triethylene glycol polyurethane dendrimer synthesis 29 27. 1,4-bis(2-hydroxyisopropyl)benzene polyurethane dendrimer synthesis 30 28. 2-butyne-1,4-diol polyurethane dendrimer synthesis 31 ix 29. 2-butyne-1,4-diol polyurethane dendrimer synthesis 32 30. Mechanism of Curtius rearrangement 34 31. Synthetic strategies of alkene wedge and dendrimers 47 32. Synthesis of polyurethane wedge with ally periphery initial model A 48 33. Synthesis of polyurethane wedge with ally periphery initial model B 50 34. Synthesis of branching monomer 52 35. Synthesis of polyurethane wedge with allyl periphery 53 1 13 36. H and C NMR spectrum of 11 in CDCl3-d1 55 37. Synthesis of polyurethane dendrimer with allyl periphery 56 38. Synthesis of polyurethane wedge with pentene periphery 64 1 39. H NMR spectrum of 20 in CDCl3-d1 65 13 40. C NMR spectrum of 21 in CDCl3-d1 65 41. Thiol-ene “click” chemistry of polyurethane wedge 66 1 42. H NMR spectrum of 22 in CDCl3-d1 67 43. Synthesis of polyurethane dendrimers 68 44. 4,4'-MDI and 4,4'-biphenyldicarboxylic acid 68 45. Synthesis of polyurethane dendrimers from trimesic acid 96 46. Synthesis of dendrimers 70 47. Synthesis of polyurethane dendrimers from sebacic acid as ester core 71 48. Synthesis of polyurethane dendrimers from porphyrin as ester core 73 49. Synthetic strategies of alkyne wedge and dendrimers 82 50. Synthesis of first generation wedge with propargyl periphery 83 1 13 51. H and C NMR spectrum of 4 in CDCl3-d1 84 52. Synthesis of second generation wedge with propargyl periphery 85 53. Synthesis of first generation of polyurethane with propargyl periphery 86 54. Synthesis of first generations polyurethane dendrimers 87 55. Synthesis of first and second generation polyurethane wedge with pentyne periphery 91 1 56. H NMR spectrum of 8 in CDCl3-d1 92 57. Synthesis of first generation wedge click reaction with 4-azidobenzoic acid 93 x 58. Synthesis of first and second generation wedge click reaction with phenyl boronic acid 94 1 13 59. H and C NMR spectrum of 12 in CDCl3-d1 95 60. Synthesis of first generation wedge click reaction with 3-azido-7-hydroxycoumarin 96 61. Synthesis of polyurethane dendrimers from trimesic acid 98 62.
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