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The Attempted Synthesis of a Thiazolidinedione-Containing THE ATTEMPTED SYNTHESIS OF A THIAZOLIDINEDIONE-CONTAINING LIGAND FOR VANADYL COMPLEXATION: INVESTIGATING POTENTIAL SYNERGISTIC INSULIN MIMICS by Devin Paul Mitchell B.Sc. (Hons.), McGill University, Canada, 1997 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE in THE FACULTY OF GRADUATE STUDIES (Department of Chemistry) We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA November 1999 © Devin Paul Mitchell, 1999 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department or by his or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of cC-Af/H/i//v The University of British Columbia Vancouver, Canada Date hjei/ f is/11 DE-6 (2/88) ABSTRACT Thiazolidinedione-containing compounds are a relatively recent class of oral hypoglycemic agents used today to treat type II diabetes mellitus. Vanadium is well known to be an effective agent for lowering blood-glucose levels. In this study, synthesis of the ligand precursors 5-[4-(3-hydroxypropoxy)benzyl]-2,4- thiazolidinedione (HPBT), 5-[4-(3-bromopropoxy)benzyl]-2,4-thiazolidinedione (BPBT), and 5-[4-(3-iodopropoxy)benzyl]-2,4-thiazolidinedione (IPBT) were accomplished at high purity in gram scale quantities. These were fully characterized by the methods mentioned below. Several synthetic pathways were examined, with varying success; 5-[4-(3-p- toluenesulfonylpropoxy)benzyl]-2,4-thiazolidinedione (TsPBT), N-BOC-5-[4-(3- hydroxypropoxy)benzyl]-2,4-thiazolidinedione (BocHPBT), N-BOC-5-[4-(3- iodopropoxy)benzyl]-2,4-thiazolidinedione (BocIPBT), and 5-[4-(3- sulfonylimidazolepropoxy)benzyl]-2,4-thiazolidinedione (ImPBT) were compounds on those pathways. 5-[4-(3-Acetyl-6-hexoxy-2-one)benzyl]-2,4-thiazolidinedione (APBT), was synthesized, but not successfully purified. The vanadium coordination complex, bis-(5-[4-(3-acetyl-6-hexoxy-2-one)benzyl]-2,4-thiazolidinedionato) oxovanadium VO(APBT)2) gave encouraging preliminary results, e.g., synthesis of the complex directly from IPBT and vanadyl acetylacetonate; however further purification of the ligand would be required to determine stability constants. The ligand precursors were characterized by [H NMR spectroscopy, mass 13 spectrometry, elemental analyses, infrared spectroscopy and, in certain instances, C ii NMR spectroscopy and two dimensional NMR spectroscopy for HPBT and IPBT. BocHPBT was characterized as a pure compound with !H NMR spectroscopy. TsPBT, BocIPBT and ImPBT were not purified enough for complete characterization. LSIMS characterization of the thiazolidinedione oxovanadium(IV) complex, VO(APBT)2, indicated that the synthetic pathway so far elucidated could ultimately be refined to yield this compound in greater purity and quantity. iii TABLE OF CONTENTS page Abstract ii Table of Contents iv List of Figures vi List of Tables viii List of Abbreviations ix Acknowledgements xiii Chapter 1 Introduction xiii 1.1 Diabetes Mellitus 1 1.2 Vanadium Background. 2 1.3 Insulin-Mimetic Effects of Vanadium 3 1.4 Thiazolidinediones 5 1.5 Research Focus 8 Chapter 2 Experimental 10 2.1 Materials 10 2.2 Instrumentation 11 2.3 Procedures 11 2.4 Synthesis: Reactions Accomplished 12 2.5 Synthesis: Reactions Attempted. 19 Chapter 3 Results and Discussion 27 3.1 Design and Syntheses 27 iv 3.2 Characterization 38 Chapter 4 Conclusions and Future Directions 49 4.1 Conclusions 49 4.2 Future Directions 50 References 53 v LIST OF FIGURES page Figure 1.1 Bis(maltolato)oxovanadium(IV) (BMOV) 4 Figure 1.2 Chemical structures of various thiazolidinediones 5 Figure 1.3 5-[4-(3-Acetyl-6-hexoxy-2-one)benzyl]-2,4-thiazolidinedione (APBT) and its target vanadyl complex (VO(APBT)2) 9 Figure 2.1 Schematic diagram of a dry flash column 12 Figure 3.1 Synthesis of 4-(3-hydroxypropoxy)benzaldehyde 27 Figure 3.2 Overall scheme for the reactions described in this thesis 28 Figure 3.3 Synthesis of 5-([4-(3-hydroxypropoxy)phenyl]methylene)-2,4- thiazolidinedione (oxidized HPBT) 29 Figure 3.4 Synthesis of 5-[4-(3-hydroxypropoxy)benzyl]-2,4-thiazolidinedione (HPBT) 30 Figure 3.5 Synthesis of 5-[4-(3-bromopropoxy)benzyl]-2,4-thiazolidinedione (BPBT).. 31 Figure 3.6 Synthesis of 5-[4-(3-iodopropoxy)benzyl]-2,4-thiazolidinedione (IPBT) 32 Figure 3.7 Synthesis of A^-BOC-5-[4-(3-hydroxypropoxy)benzyl]-2,4-thiazolidinedione (BocHPBT) 32 Figure 3.8 Synthesis of A^A^'-sulfuryldiimidazole 33 Figure 3.9 Synthesis of 5-[4-(3-acetyl-6-hexoxy-2-one)benzyl]-2,4-thiazolidinedione (APBT) 34 Figure 3.10 Synthesis of 5-[4-(3-/7-toluenesulfonylpropoxy)benzyl]-2,4-thiazolidinedione (TsPBT) 35 vi Figure 3.11 Synthesis of A^-BOC-5-[4-(3-iodopropoxy)benzyl]-2,4-thiazolidinedione (BocIPBT) 36 Figure 3.12 Synthesis of N-BOC-2,4-thiazolidinedione 36 Figure 3.13 Synthesis of 5-[4-(3-sulfonylimidazolepropoxy)benzyl-2,4-thiazolidinedione (ImPBT) 37 Figure 3.14 Synthesis of bis-(5-[4-(3-acetyl-6-hexoxy-2-one)benzyl]-2,4- thiazolidinedionato) oxovanadium (VO(APBT)2) 38 Figure 3.15 Selected FTIR spectra comparing various ligand precursors 40 Figure 3.16 Regions of *H NMR (200 MHz) spectra of various precursor compounds .. 42 Figure 3.17 !H-NMR spectra (200 MHz) of BocHPBT 43 Figure 3.18 13C NMR (125 MHz) spectrum of HPBT with assignments 45 Figure 3.19 13C NMR (75 MHz) spectrum of IPBT with assignments 45 Figure 3.20 HMQC spectrum of HPBT 46 Figure 3.21 HMQC spectrum of IPBT 47 Figure 3.22 VO(APBT)2 mass spectrum (LSIMS) 48 Figure 4.1 Synthesis of APBT using BOC protected IPBT 50 Figure 4.2 Synthesis of APBT using ImPBT 51 Figure 4.3 Synthesis of the desired complex (VO(APBT)2) from APBT and VOS04 .... 51 vii LIST OF TABLES page Table 2.1 Variations in conditions for acetylacetone reaction 20 Table 3.1 Characteristic IR absorptions (cm"1) of ligand precursors 39 Table 3.2 Characteristic IR absorptions (cm"1) of N'-sulfuryldiimidazole 40 viii LIST OF ABBREVIATIONS Abbreviation Meaning acac acetylacetone AIDS Acquired Immune Deficiency Syndrome Anal. Analysis APBT 5 - [4-(3 -acetyl-6-hexoxy-2-one)benzyl] -2,4- thiazolidinedione APT attached proton test ATPase adenosine triphosphatase BMOV bis(maltolato)oxovanadium(IV) BOC butyloxycarbonyl BocHPBT N-BOC-5-[4-(3-hydroxypropoxy)benzyl]-2,4- thiazolidinedione BocIPBT N-BOC-5- [4-(3 -iodopropoxy)benzyl] -2,4-thiazolidinedione (Boc)20 di-terr-butyl dicarbonate BPBT 5 - [4-(3 -bromopropoxy)benzyl] -2,4-thiazolidinedione Calc. Calculated °C degrees Celsius CDCI3 deuterated chloroform CD3OD deuterated methanol cm centimeter cm"1 wave number ix d doublet dd doublet of doublets 5 chemical shift (ppm, NMR) A heat DMAP 4-(dimethylamino)pyridine DMF N,N-dimethylformamide EI electron-impact ionization eq equivalents EtOH ethanol FDA Food and Drug Administration (U.S.) FTIR fourier transform infrared g gram GI gastrointestinal GLUT-4 insulin-activated transporter protein HMQC heteronuclear multiple quantum coherence HPBT 5-[4-(3-hydroxypropoxy)benzyl]-2,4-thiazolidinedione HPLC high performance liquid chromatography hr hour IDDM insulin-dependent diabetes mellitus ImPBT 5-(3-sulfonylimidazolepropoxy)benzyl)-2,4- thiazolidinedione IPBT 5-[4-(3-iodopropoxy)benzyl]-2,4-thiazolidinedione IR infrared x LD50 dose of a substance at which 50% of subjects die LSIMS liquid secondary ion mass spectrometry m multiplet M moles/liter [M]+ positively charged parent mass MHz megahertz mL milliliter mmol millimole mol mole MS mass spectrometry m/z mass-to-charge ratio NIDDM non-insulin-dependent diabetes mellitus NMR nuclear magnetic resonance v stretching vibration (IR) oxidized HPBT 5-([4-(3-hydroxypropoxy)phenyl]methylene)-2,4- thiazolidinedione % percent p para pH negative log of the concentration of H3<_)+ pKa negative log of the deprotonation constant PPAR peroxisome proliferator activated receptor PPARy peroxisome proliferator activated receptor gamma PPI13 triphenylphosphine xi PPb.3«Br2 dibromotriphenylphosphine ppm parts per million PTPase protein tyrosine phosphatase RXR retinoid X receptor s singlet STZ streptozotocin t triplet temp temperature tert tertiary THF tetrahydrofuran TLC thin layer chromatography Ts j!?-toluenesulfonate TsPBT 5-[4-(3-p-toluenesulfonylpropoxy)benzyl]-2,4- thiazolidinedione tt triplet of triplets UV-vis ultraviolet-visible VOL2-2H vanadyl with two deprotonated ligands attached VO(acac)L-H vanadyl with one deprotonated ligand and one acetylacetonate ligand attached VO(APBT)2 bis-(5- [4-(3 -acetyl-6-hexoxy-2-one)benzyl] -2,4- thiazolidinedionato)oxovanadium(IV) xii ACKNOWLEDGMENTS The first person to whom I owe thanks is without a doubt Dr. Chris Orvig, who, was patient and understanding. His guidance and encouragement was invaluable and immensely appreciated. The past and present Orvig group members helped make this research project very memorable. Peter especially took me under his wing at the beginning and led me into my project. I felt that the group dynamics were very positive and that there was always somebody who would be willing to help. Plenty of non-Orvig group chemistry people helped in myriad ways and I would like to list them all by name but there are just too many. I would especially like to thank my family and Karycia for their loving support. My friends in organic chemistry were life-savers when it came time to find new directions of research. Thanks. Prof. R. V. Stick was extremely helpful and I appreciate the time he took out of his schedule to help lend his experience to my research. I would also like to thank Mr. Peter Borda for completing the elemental analyses and the UBC Chemistry support staff for their assistance in navigating the bureaucracy of UBC.
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