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Exploration of Synthetic Routes to the Sulfoxide and Sulfone Derivatives of Benzotrithiophenes

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Exploration of Synthetic Routes to the Sulfoxide and Sulfone Derivatives of Benzotrithiophenes Wright State University CORE Scholar Browse all Theses and Dissertations Theses and Dissertations 2008 Exploration of Synthetic Routes to the Sulfoxide and Sulfone Derivatives of Benzotrithiophenes Tiffany M. Hall Wright State University Follow this and additional works at: https://corescholar.libraries.wright.edu/etd_all Part of the Chemistry Commons Repository Citation Hall, Tiffany M., "Exploration of Synthetic Routes to the Sulfoxide and Sulfone Derivatives of Benzotrithiophenes" (2008). Browse all Theses and Dissertations. 862. https://corescholar.libraries.wright.edu/etd_all/862 This Thesis is brought to you for free and open access by the Theses and Dissertations at CORE Scholar. It has been accepted for inclusion in Browse all Theses and Dissertations by an authorized administrator of CORE Scholar. For more information, please contact [email protected]. EXPLORATION OF SYNTHETIC ROUTES TO THE SULFOXIDE AND SULFONE DERIVATIVES OF BENZOTRITHIOPHENES A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science By TIFFANY M. HALL B.S., Wright State University, 2006 2008 Wright State University WRIGHT STATE UNIVERSITY SCHOOL OF GRADUATE STUDIES July 30, 2008 I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY SUPERVISION BY Tiffany M. Hall ENTITLED Exploration of synthetic routes to the sulfoxide and sulfone derivatives of Benzotrithiophenes BE ACCEPTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF Master of Science . ______________________________ Eric Fossum, Ph.D. Thesis Director ______________________________ Kenneth Turnbull, Ph.D. Department Chair Committee on Final Examination _________________________________ Eric Fossum, Ph.D. _________________________________ Kenneth Turnbull, Ph.D. _________________________________ David A. Dolson, Ph.D. _________________________________ Joseph F. Thomas, Jr., Ph.D. Dean, School of Graduate Studies ABSTRACT Hall, Tiffany M. M.S., Department of Chemistry, Wright State University, 2008. Exploration of synthetic routes to the sulfoxide and sulfone derivatives of Benzotrithiophenes. The synthesis of new organic materials that have the potential to be utilized in a thermoelectric application are in demand because they are able to convert thermal energy directly into electrical energy. The “end-on” sulfoxide and sulfone derivatives of Benzo[1,2-c:3,4-c’:5,6-c”]trithiophene 1 were synthesized for this reason. The “end-on” mode sulfoxide derivative 13 of Benzo[1,2-c:3,4-c’:5,6-c”]trithiophene 1 was prepared by utilizing 3-Carboxypyridinium Chlorochromate (CPCC) 16 and AlCl 3, as an oxidizing 1 system. The H NMR (DMSO-d6) spectrum displayed a singlet peak at 5.03 ppm, and the IR spectrum displayed an absorption at 1059.33cm -1, which confirmed its structure. The “end-on” mode sulfone derivative 14 was completed by a two step process: 1) oxidation of Benzo[1,2-c:3,4-c’:5,6-c”] tris-(tetrahydrothiophene) 5 followed by 2) aromatization using DDQ in chlorobenzene. Verification of the compound’s structure was achieved via 1 its H NMR (DMSO-d6) spectrum that displayed a single peak at 6.5 ppm, which is in close approximation to the 6.64 ppm estimation. iii TABLE OF CONTENTS Page INTRODUCTION......................................................................................................1 HISTORICAL ............................................................................................................3 Thermoelectrics..........................................................................................................3 Seebeck Effect ......................................................................................................4 Peltier Effect.........................................................................................................7 Thomson Effect ....................................................................................................9 Efficiency: Figure-of-Merit (Z)..................................................................................11 Semiconductors, Metals/Metal Alloys..................................................................12 Thermoelectric Sensitivity ...................................................................................15 Applications: Generation and Refrigeration ...............................................................17 Types of Generators: Isotopic and Non-Isotopic...................................................17 Refrigeration Common Materials.........................................................................19 Inorganic Materials vs. Organic Materials..................................................................21 Past Research ............................................................................................................23 This Project ...............................................................................................................24 iv TABLE OF CONTENTS (CONTINUED) Page EXPERIMENTAL ....................................................................................................25 Instrumentation and Chemicals ............................................................................25 Benzo[1,2-c:3.4-c’:5,6-c”]tris(tetrahydrothiophene) 5..........................................25 Modified Step of Benzo[1,2-c:3.4-c’:5,6-c”]tris(tetrahydrothiophene) 5...............26 Benzo[1,2-c:3.4-c’:5,6-c”]trithiophene 1..............................................................27 New Approach to Benzo[1,2-c:3.4-c’:5,6-c”]trithiophene 1 .................................27 3-Carboxypyridinium Chlorochromate (CPCC) 16 ..............................................28 3-Carboxypyridinium Chlorochromate (CPCC)/AlCl 3 Oxidation Reaction 13......29 3-Carboxypyridinium Chlorochromate (CPCC)/AlCl 3 Oxidation Reaction 14......30 Dichloromethane and m-CPBA Oxidation Reaction of Trithiophene at r.t............30 Dichloromethane and m-CPBA Oxidation Reaction of Trithiophene at reflux......30 Chloroform and m-CPBA Oxidation Reaction of Trithiophene (1:1) at r.t............31 Chloroform and m-CPBA Oxidation Reaction of Trithiophene (7:1) at r.t ...........31 Chloroform and m-CPBA Oxidation Reaction of Trithiophene (7:1) at reflux......31 Acetone and m-CPBA Oxidation Reaction of Trithiophene (7:1) at r.t .................31 Acetone and m-CPBA Oxidation Reaction of Trithiophene (7:1) at 50 oC.............32 Methanol and ZrCl 4/30% H 2O2 Oxidation Reaction of Trithiophene at r.t ............32 Et 2O/Acetone and 30% H 2O2 Oxidation Reaction of Trithiophene at r.t ...............32 Alternative Approach: Oxidation prior to Aromatization 33 Alternative Approach: Aromatization to yield the sulfone derivative 14 34 3-Bromo-2,3’-bithiophene 10 ...............................................................................34 2,3’:2’,3”- terthiophene 12 ...................................................................................35 v TABLE OF CONTENTS (CONTINUED) Page RESULTS AND DISCUSSION ................................................................................37 CONCLUSIONS.......................................................................................................68 REFERENCES..........................................................................................................75 VITA.........................................................................................................................81 vi LIST OF FIGURES Figure Page 1. U.S. Electric Power Industry Net Generation 2006 ...........................................2 2. Seebeck Effect Thermocouple: Generate Electricity..........................................5 3. Peltier Effect Thermocouple: Thermoelectric Cooling. .....................................8 4. Thomson Effect Thermocouple........................................................................10 5. Thermoelectric Materials Selection..................................................................14 6. Figure-of Merit for typical thermoelectric Materials.. ......................................21 7. Conjugated aromatic polymer system ..............................................................23 8. Structures of benzotrithiophene derivatives 1, 2, and 3. ...................................24 1 9. H NMR (CDCl 3) spectrum of Benzo[1,2-c:3,4-c’:5,6-c”]tris (tetrahydrothio- phene) 5 ..........................................................................................................38 1 10. H NMR (CDCl 3) spectrum of Benzo[1,2-c:3,4-c’:5,6-c”]trithiophene 1 Pre- Column ...........................................................................................................40 1 11. H NMR (CDCl 3) spectrum of Benzo[1,2-c:3,4-c’:5,6-c”]trithiophene 1 Post- Column ...........................................................................................................40 13 12. C NMR (CDCl3) spectrum of Benzo[1,2-c:3,4-c’:5,6-c”]trithiophene 1.........41 1 13. H NMR (CDCl 3) spectrum of the Alternative Approach of Benzo[1,2-c:3,4- c’:5,6-c”]trithiophene 1 ...................................................................................42 1 14. H NMR (CDCl 3) spectrum of the Alternative Approach of Benzo[1,2-c:3,4- c’:5,6-c”]trithiophene after column chromatography........................................43 13 15. C NMR (CDCl 3) spectrum of the Alternative Approach of Benzo[1,2-c:3,4- c’:5,6-c”]trithiophene after column..................................................................44 1 16. H NMR (CDCl 3) spectrum of the Alternative Approach of Benzo[1,2-c:3,4-
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