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The Synthesis of 2-(1-Indenyl)-Phenol

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The Synthesis of 2-(1-Indenyl)-Phenol Eastern Illinois University The Keep Masters Theses Student Theses & Publications 2003 The yS nthesis of 2-(1-Indenyl)-phenol: A Potential Ligand For Metallocene Polymerization Catalysts; and, ω-Iodoalkyl(methyl) Malonate Esters: Synthesis and Application in Bioconjugate Chemistry Sara E. Bendler Eastern Illinois University This research is a product of the graduate program in Chemistry at Eastern Illinois University. Find out more about the program. Recommended Citation Bendler, Sara E., "The yS nthesis of 2-(1-Indenyl)-phenol: A Potential Ligand For Metallocene Polymerization Catalysts; and, ω- Iodoalkyl(methyl) Malonate Esters: Synthesis and Application in Bioconjugate Chemistry" (2003). Masters Theses. 1423. https://thekeep.eiu.edu/theses/1423 This is brought to you for free and open access by the Student Theses & Publications at The Keep. It has been accepted for inclusion in Masters Theses by an authorized administrator of The Keep. For more information, please contact [email protected]. THESIS/FIELD EXPERIENCE PAPER REPRODUCTION CERTIFICATE TO: Graduate Degree Candidates (who have written formal theses) SUBJECT: Permission to Reproduce Theses The University Library is receiving a number of request from other institutions asking permission to reproduce dissertations for inclusion in their library holdings. Although no copyright laws are involved, we feel that professional courtesy demands that permission be obtained from the author before we allow these to be copied. PLEASE SIGN ONE OF THE FOLLOWING STATEMENTS: Booth Library of Eastern Illinois University has my permission to lend my thesis to a reputable college or university for the purpose of copying it for inclusion in that insti_tition's lib.cary OY{esearch ho}dings. Date I respectfully request Booth Library of Eastern Illinois University NOT allow my thesis to be reproduced because: Author's Signature Date :nes1s4 torm The Synthesis of 2-(1-Indenyl)-phenol: A Potential Ligand For Metallocene Polymerization Catalysts AND w-Iodoalkyl(methyl) Malonate Esters: Synthesis and Application in Bioconjugate Chemistry Sara E. Bendler Eastern Illinois University Certificate of Comprehensive Knowledge For The Awarding Of A Graduate Degree Department of Chemistry Eastern Illinois University We certify that Sara E • Bendler SS# has successfully lemonstrated comprehension of her/his field of study and recommend that the degree Master of science in Chemistry >e awarded. Date ~ Ma(}1 J}CJD3 THE GRf\GU.r\TE SCHOOL ---·--·-----··--EASH i<N ill i'VJ:S l1N'\'[ RSITY-- Table of Contents Acknowledgements ........................................................................... i List of Figures .................................................................................. ii List of Tables .................................................................................. iii List of Schemes ............................................................................... .iv List of Abbreviations .......................................................................... v Chapter I: The Synthesis of 2-(1-indenyl)-phenol: A Potential Ligand for Metallocene Polymerization Catalysis Abstract ............................................................................... 1 Section I. Introduction ......................................................... 2 Section II. Results and Discussion ............................................ 11 Section III. Future Research .................................................... 14 Section IV. Experimental. ....................................................... 15 Section V. References ........................................................... 18 Chapter II: ro-Iodoalkyl(methyl) Malonate Esters: Synthesis and Application in Bioconjugate Chemistry Abstract .............................................................................. 19 Section I. Introduction ........................................................ 20 Section II. Results & Discussion ............................................ 33 Section III. Future Research .................................................. .40 Section IV. Experimental ...................................................... 42 Section V. References ......................................................... 50 Appendix List of Appendix Figures ............................................................. 52-53 Appendix Figures ..................................................................... 54-75 Published Research ................................................................... 76-84 Acknowledgements I would like to begin with thanking collaborators Nicloe Orwar, Diana Davis, and Sarah Clark, who helped install the foundation for the second section of this research. The work I have done is one section of a larger project, and each of these collaborators have also made important advancements toward the realization of the final research goal, a new therapeutic compound. I would also like to thank the external funding which made this research possible. The second section of research was supported through a NIH Grant, and I was supported through a Sidney R. Steele Summer Stipend Award. Additionally, I would like to thank Eastern Illinois University for the graduate assistantship which helped support me during my two years here in the masters' program. Finally, I would like to thank the members of my thesis committee: Dr. Norbert Furumo, Dr. Barbara Lawrence, Dr. Edward Treadwell, and Dr. Robert Chesnut. Thank you all for your time, assistance, and suggestions. Special recognition goes to Dr. Robert Chesnut, my research advisor, for being so actively involved with the research and preparation of this thesis. His patience, knowledge, and sense of humor make him an important asset to the Department of Chemistry. List of Figures Figure 1.1 Stereoisomers of Polypropylene Figure 1.2 Metallocene Catalysis: Part I Figure 1.3 Metallocene Catalysis: Part II Figure 1.4 Metallocene Catalysis: Part III Figure 1.5 Rae- and Mesa-like Isomers of (2-Phlndh ZrP+ Figure 1.6 Mono-Cyclopentadienyl-Amido Catalysts Figure 1.7 (TCP)H2 in Titanium and Zirconium Complexes Figure 1.8 Titanium Complexes of Rothwell Ligand Figure 2.1 Structure of Tamoxifen Figure 2.2 Domains of The Nuclear Receptor Superfamily Figure 2.3 High-affinity Ligands for the Estrogen Receptor Figure 2.4 Rotation of Estradiol About a Pseudo-C2 Axis Figure 2.5 Structures of Cisplatin and Carboplatin Figure 2.6 Structural Comparison of Proposed Therapeutic Agent with Clinically­ Used Platinum Compounds Figure 2.7 Target Therapeutic Compound Figure 2.8 General Structure of Linkage Molecules Figure 2.9 Target Compound with Uniform Benzyl Protection 11 List of Tables Table 1 Reaction Optimization for the Synthesis ofTHP-protected 2-Bromophenol Table 2.1 TLC Analysis for Crude Diisoamyl-6-iodohexyl(methyl) Malonate (10) Table 2.2 TLC Analysis for Crude Diisoamyl-10-iododecyl(methyl) Malonate (11) Table 2.3 1H NMR,Proton Assignment for Isoamyl Esters Table 2.4 1H NMR Proton Assignment for Benzyl Esters lll List of Schemes Scheme 1.1 Kim Synthesis of 2-(1-Indenyl)-Phenol (14) Scheme 1.2 Proposed Synthesis of 2-(1-Indenyl)-Phenol (14) Scheme 1.3 Synthesis ofTHP-Protected 2-Bromophenol (17) Scheme 1.4 Synthesis of 2-(1-Indenyl)-Phenol (14) Scheme 2.1 Proposed Synthesis of Diisoamyl(methyl) Malonate (9) Scheme 2.2 Proposed Synthesis of Diisoamyl-6-iodohexyl(methyl) Malonate (10) Scheme 2.3 Proposed Synthesis of Diisoamyl-6-iododecyl(methyl) Malonate (11) Scheme 2.4 Proposed Synthesis of Alkylated Estradiol (14) Scheme 2.5 Proposed Reduction of Steroidal Ketone (15) Scheme 2.6 Proposed Synthesis of Dibenzyl(methyl) Malonate (17) Scheme 2.7 Proposed Synthesis of Dibenzyl-10-iododecyl(methyl) Malonate (18) Scheme 2.8 Synthesis of Diisoamyl(methyl) Malonate (9) Scheme 2.9 Synthesis of Diisoamyl-6-iodohexyl(methyl) Malonate (10) Scheme 2.10 Synthesis of Diisoamyl-10-iododecyl(methyl) Malonate (11) Scheme 2.11 Synthesis of 7-Alpha Alkylated Estradiol (14) Scheme 2.12 Synthesis of Dibenzyl(methyl) malonate (17) Scheme 2.13 Synthesis ofDibenzyl-10-iododecyl(methyl) Malonate (18) Scheme 2.14 Proposed Realization of Uniform Benzyl Protection IV List of Abbreviations Cyclopentadienyl anion Cp Nuclear Magnetic Resonance NMR Trimethyl Aluminum TMA Methyl Aluminoxane MAO Cyclopentadienyl-Amido CpA 2-(Tetramethylcyclopentadienyl)-4-methylphenol (TCP)H2 Estrogen Receptor ER Selective Estrogen Receptor Modulators SERMs Deoxyribonucleic Acid DNA N ,N-Dimethylformamide DMF Thin-Layer Chromatography TLC Infared Spectroscopy IR Low Resolution Mass Spectroscopy LRMS Tetrahydrofuran THF v Chapter I Abstract Metallocene catalysis is an important division of polymerization chemistry. The design of appropriate ligands for metallocene catalysts has focused on stereochemical control and structural diversity. The synthesis of the potential ligand 2-(1-indenyl)­ phenol has been developed. Indenyl phenol ligands offer advancements over cyclopentadienyl ligands because the steric and electronic properties of the catalyst could be tailored to suit individual polymerization reactions. 2-(1-Indenyl)-phenol was synthesized with an overall yield of 4% and characterized with 1H NMR and 13C NMR. 1 Chapter I: Section I Introduction Advancements and developments in polymer chemistry have supplied the world with a variety of household and industrial products. Many common products, from dishwasher-safe food containers to indoor-outdoor carpeting, are realized through the advancement of polymer chemistry, specifically
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