Jozef Hodyl PhD Thesis - Theses - Flinders University

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CHAPTER 2SYNTHESIS OF MACROCYCLIC RECEPTORPRECURSORS2.1 Synthetic design strategyAs indicated in the Introduction, the synthetic protocol formulated for the firstgeneration of tetra-N-substituted, phenoxy derived, cyclen-based receptors,exemplified by 26, is quite straightforward.26Finding a synthetic protocol for the silica immobilised receptors 94 - 96, shownbelow, that are the objects of this investigation is necessarily more complex sincethere are two types of pendant arm to be attached to the macrocycle; the linker arm,to connect the receptor to the silica surface, and the three arms that ultimatelyconstitute the walls of the anion binding cavity.94, R = H95, R = (OCH 2 CH 2 ) 2 OH96, R = (OCH 2 CH 2 ) 3 OH35
In addition, successful immobilisation of these receptors on a silica surfacecomplicates the characterisation of the guest uptake process. 136 In particular, thesilica immobilised receptor materials cannot be quantitated to obtain bindingconstants as this requires dissolution of both the host and the guest to set upconditions for a rapidly established equilibrium between the bound and free guest. 165Taking this point into account, it was decided firstly to synthesise a structurally andchemically similar model receptor, 49, that could be used to test the suitability of athree-walled binding cavity. In this molecular receptor model the place of the linkergroup would be taken by an (S)-hydroxypropyl pendant arm, as shown in Figure 2.1,and because of its solubility anion binding constants could be measured andcompared with those found for a comparable first generation receptor such as 26.49Figure 2.1 Schematic depiction of the structural features of the molecular receptor model, 49,highlighting its correspondence with silica attached receptor 94: blue, three phenoxyderived pendant arms, red, octa-coordination with cadmium(II) and green, (S)-hydroxypropyl pendant arm, simulating the linker group.Conceptually, the three-walled cavity appears to have an "open gate" throughwhich included species are likely to escape through increased contact with thesolvent. Furthermore, the reduction in the number of aromatic species forming thewalls of the cavity may result in a proportional loss of possible π-π interactions,presupposing, of course, that hydrogen bonding interactions between the host O-H36
Page 1 and 2: Silica Immobilised MetalIon Activat
Page 3 and 4: ABSTRACTImmobilisation of functiona
Page 5: DECLARATIONI certify that this thes
Page 8 and 9: EtOHGPDMSGPDMESGPSGPTSethanolglycid
Page 10: CHAPTER ONEINTRODUCTION
Page 13 and 14: The focus of this work was to prepa
Page 15 and 16: sequestering anions has proved to b
Page 17 and 18: ange of pH due to its high basicity
Page 19 and 20: nitrophenol or p-nitrophenolate wit
Page 21 and 22: It has been shown by NMR and crysta
Page 23 and 24: within the cavity of a p-tert-butyl
Page 25 and 26: 60 in 0.5% DMSO-MeCN (v/v). 82 The
Page 27 and 28: synthesised bi- tri- and tetra - π
Page 29 and 30: adopt a trans-III conformation, whe
Page 31 and 32: amide oxygen atoms on the pendant a
Page 33 and 34: apparent there is, nonetheless, evi
Page 35 and 36: However, hetero-N-substitution on t
Page 37 and 38: Si-OH +- OH SiO - + H 2 OFor surfac
Page 39 and 40: 35This material was obtained with a
Page 41 and 42: OOSiOHOROR OSiOHOOOSiOSiOSiOSiOSiOS
Page 43 and 44: Tetraaza metal complexes immobilise
Page 45: CHAPTER TWOSYNTHESIS OF MACROCYCLIC
Page 49 and 50: 3233Figure 2.3Reaction of 3-(glycid
Page 51 and 52: The methodology chosen was adapted
Page 53 and 54: agreed with literature values. 109R
Page 55 and 56: XS HO O H61, n = 262, n = 3n+ClOSO6
Page 57 and 58: anhydrous ethanol, Scheme 2.7. The
Page 59 and 60: 75Figure 2.5 Structure of (S)-(-)-p
Page 61 and 62: metal ion coordination the pendant
Page 63 and 64: CHAPTER THREEGUEST MOLECULE INCLUSI
Page 65 and 66: 3.1 where K A is the association, o
Page 67 and 68: 0.5cχG∆δ∆δGbaχ GFigure 3.1S
Page 69 and 70: χG∆δ∆δGFigure 3.4 Job's Plot
Page 71 and 72: The downfield movement of the guest
Page 73 and 74: arm framework. The relative magnitu
Page 75 and 76: This phenomenon correlates well wit
Page 77 and 78: non-classical hydrogen bonding is g
Page 79 and 80: The full set of logK values obtaine
Page 81 and 82: such that they would indicate precl
Page 83 and 84: CHAPTER 4MODIFICATION OF THE SILICA
Page 85 and 86: Chemical modification of the silica
Page 87 and 88: GPTSGPDMESFigure 4.4Schematic depic
Page 89 and 90: GPS, 33, linker material with an ex
Page 91 and 92: free νOHτSiOHνSi-O-SiδH 2 Oasym
Page 93 and 94: 224, 225the surface silanol groups.
Page 95 and 96: esonances, the spectrum for Si-GPS-
Page 97 and 98:
increase in surface coverage from t
Page 99 and 100:
and, more so due to the larger size
Page 101 and 102:
CHAPTER 5METAL ION UPTAKE STUDIES W
Page 103 and 104:
Scheme 5.1 Metal(II) ion coordinati
Page 105 and 106:
linker material, Si-GPS, 33; endcap
Page 107 and 108:
[Cd(Trac)](ClO 4 ) 2 , 94, or Si-GP
Page 109 and 110:
CHAPTER 6GUEST MOLECULE INCLUSION S
Page 111 and 112:
and D-histidinate. Guest inclusion
Page 113 and 114:
Table 6.2Percent inclusion data for
Page 115 and 116:
contains two hydroxy groups in the
Page 117 and 118:
methoxy group, as portrayed by the
Page 119 and 120:
these guest molecules with receptor
Page 121 and 122:
only about half of that taken up by
Page 123 and 124:
Percent inclusion values for these
Page 125 and 126:
Table 6.7Percent guest inclusion of
Page 127 and 128:
6.1.7 Guest inclusion studies with
Page 129 and 130:
A1 3542Neutral GuestBAnionic GuestH
Page 131 and 132:
A1 46 7532 Anionic Guest8BCHostHost
Page 133 and 134:
extent, meta-positioned hydroxy gro
Page 135 and 136:
δ obs (ppm)6.2146.2136.2126.2116.2
Page 137 and 138:
CHAPTER 7EXPERIMENTAL7.1 General Ex
Page 139 and 140:
inding constants (logK values) and
Page 141 and 142:
delay time of 4 s. 13 C CPMAS NMR s
Page 143 and 144:
C, -CH 2 - CH 2 OSO 2 ); 68.11 (1 C
Page 145 and 146:
A solution of 69 (2.00 g, 10.1 mmol
Page 147 and 148:
Bn, meta); 127.79 (1 C, Bn, para);
Page 149 and 150:
added in a single portion. The mixt
Page 151 and 152:
dioxane): δ 158.67 (1 C, C=O); 135
Page 153 and 154:
1-(benzyloxycarbonyl)-4,7,10-tris-(
Page 155 and 156:
1,4,7-tris-((S)-2-hydroxy-3-phenoxy
Page 157 and 158:
1,4,7-tris(S)-2-hydroxy-3-[4-((2-(2
Page 159 and 160:
1,4,7-tris(S)-2-hydroxy-3-[4-(2-(2-
Page 161 and 162:
1-(2-hydroxypropyl)-4,7,10-tris-((S
Page 163 and 164:
7.11 Preparation of the silica mate
Page 165 and 166:
To a suspension of 33 (1.48 g, 1.1
Page 167 and 168:
gel-like suspension that was cooled
Page 169 and 170:
Si-GPS-Tri-Trac, 4545The title comp
Page 171 and 172:
APPENDIX ABINDING CONSTANT DETERMIN
Page 173 and 174:
1.01000.880δ obs (ppm)0.60.4logK =
Page 175 and 176:
APPENDIX BDETERMINATION OF STOICHIO
Page 177 and 178:
0.5χG∆δGFigure B.2χ GSimulated
Page 179 and 180:
13 C CPMAS NMR SPECTRA OF SOME HIGH
Page 181 and 182:
Si-GPS-[Cd(Trac)(2,5-diydroxybenzoa
Page 183 and 184:
REFERENCES
Page 185 and 186:
15. D. Tzalis and Y. Tor, Tetrahedr
Page 187 and 188:
42. A. P. Davis and R. S.Wareham, A
Page 189 and 190:
69. R. J. Bergeron, M. A. Channing
Page 191 and 192:
93. C. B. Smith, A. K. W. Stephens,
Page 193 and 194:
118. D. D. Dischino, E. J. Delaney,
Page 195 and 196:
144. X. Huang, X. Chang, Q. He, Y.
Page 197 and 198:
169. J. M. Klunder, T. Onami and K.
Page 199 and 200:
197. K. A. Connors, Binding Constan
Page 201 and 202:
221. J. Blumel, J. Am. Chem. Soc.,
Page 203:
247. W. Likussar and D. F. Botz, An
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Jozef Hodyl PhD Thesis - Theses - Flinders University

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