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The Synthesis, Reduction, and Chlorination of 5-Alkoxy-2,3-Diphenylterephthalates

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The Synthesis, Reduction, and Chlorination of 5-Alkoxy-2,3-Diphenylterephthalates Wright State University CORE Scholar Browse all Theses and Dissertations Theses and Dissertations 2011 The Synthesis, Reduction, and Chlorination of 5-alkoxy-2,3-diphenylterephthalates Rachel Marie Sayers Wright State University Follow this and additional works at: https://corescholar.libraries.wright.edu/etd_all Part of the Chemistry Commons Repository Citation Sayers, Rachel Marie, "The Synthesis, Reduction, and Chlorination of 5-alkoxy-2,3-diphenylterephthalates" (2011). Browse all Theses and Dissertations. 1046. https://corescholar.libraries.wright.edu/etd_all/1046 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]. THE SYNTHESIS, REDUCTION, AND CHLORINATION OF 5-ALKOXY-2,3-DIPHENYLTEREPHTHALATES A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science By RACHEL M. SAYERS B.S., Wright State University, 2009 2011 Wright State University WRIGHT STATE UNIVERSITY SCHOOL OF GRADUATE STUDIES June 09, 2011 I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY SUPERVISION BY Rachel M. Sayers ENTITLED The Synthesis, Reduction, and Chlorination of 5-Alkoxy-2,3-diphenylterephthalates. BE ACCEPTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF Master of Science . ______________________________ William A. Feld, Ph.D., Director Department of Chemistry College of Science and Mathematics ______________________________ Kenneth Turnbull, Ph.D., Chair Department of Chemistry College of Science and Mathematics Committee on Final Examination _________________________________ Eric Fossum, Ph.D. _________________________________ Kenneth Turnbull, Ph.D. _________________________________ William A. Feld, Ph.D. _________________________________ Andrew Hsu, Ph.D. Dean, School of Graduate Studies ABSTRACT Sayers, Rachel M. M.S., Department of Chemistry, Wright State University, 2011. The Synthesis, Reduction, and Chlorination of 5-alkoxy-2,3-diphenylterephthalates. A series of alkoxy, phenylated terephthalates has been synthesized as monomer precursors to the corresponding poly(phenylene vinylene)s (PPV). The hydroxy, phenylated terephthalate was synthesized via: 1) a Diels-Alder cycloaddition between an ethynyl boronic ester and a cyclopentadienone (CPD) with subsequent hydrolysis/oxidation of the boronate ester or 2) a Diels-Alder cycloaddition between vinylene carbonate and CPD followed by thermolysis of the bridged adduct. The hydroxy, phenylated terephthalate was alkylated via a phase-transfer reaction with iodomethane, propargyl bromide, benzyl chloride, allyl bromide, and bromobutane to produce the alkoxy, phenylated terephthalates in yields from 38.6- 91.1%. The alkoxyterephthlates were reduced with lithium aluminum hydride to either the corresponding 5-alkoxy- (methoxy, benzyloxy) or 5-hydroxy-1,4-di(hydroxymethyl)-3,4- diphenylbenzene (allyloxy, propargyloxy) in yields from 40.9-94.0%. The methoxy and benzyloxy-1,4-di(hydroxymethyl)-3,4-diphenylbenzenes were reacted with thionyl chloride to yield the corresponding 1,4-di(chloromethyl)-3,4-diphenylbenzenes. The polymerization of 5-methoxy-1,4-di(chloromethyl)-3,4-diphenylbenzene with t-BuOK yielded the insoluble polymer 5-methoxy-2,3-diphenyl-1,4-poly(phenylene vinylene). iii TABLE OF CONTENTS Page INTRODUCTION ......................................................................................................... 1 HISTORICAL ................................................................................................................ 2 PPVs via Wittig Polymerization .................................................................................... 3 Sulfonium Precursor Route (SPR) ................................................................................. 4 Xanthate Precursor Route (XPR) ................................................................................... 6 Dehydrochlorination Route (DHCL) ............................................................................. 6 Phenylated PPVs ............................................................................................................ 8 Chlorine Precursor Route (CPR) .................................................................................. 10 Alkoxy PPVs ................................................................................................................. 14 Hydroxy Phenylated Terephthlates ............................................................................... 17 Alkynylboronates .......................................................................................................... 19 Ethynylboronic acid MIDA ester .................................................................................. 21 Alkoxy Phenylated Terephthalates ............................................................................... 22 EXPERIMENTAL ........................................................................................................ 26 Instrumentation and Chemicals ............................................................................... 26 2,5-Di(ethoxycarbonyl)-3,4-diphenylcyclopentadienone 91 .................................. 27 Diethyl 5-([N-methyliminodiacetato-O,O’,N]borane)- 2,3-diphenylterephthalate 108 ................................................................................. 27 Diethyl 5-hydroxy-2,3-diphenylterephthalate 94 from 108 .................................... 28 iv TABLE OF CONTENTS (CONTINUED) Page 4,7-Bis(carboethoxy)-5,6-diphenyl-3a,7a-dihydrobenzodioxol-2-one 92 .............. 29 Diethyl 2-oxo-5,6-diphenyl-3a,7a-dihydrobenzo- [d][1,3]dioxole-4,7-dicarboxylate 93 ...................................................................... 29 Diethyl 5-hydroxy-2,3-diphenylterephthalate 94 from 92 ...................................... 30 General Procedure for the Synthesis of Diethyl 5-Alkoxy-2,3-diphenylterephthalates 111 ................................................. 30 Diethyl 5-methoxy-2,3-diphenylterephthalate 111a ............................................... 30 Diethyl 5-propargyloxy-2,3-diphenylterephthalate 111b ....................................... 31 Diethyl 5-benzyloxy-2,3-diphenylterephthalate 111c ............................................ 31 Diethyl 5-allyloxy-2,3-diphenylterephthalate 111d ................................................ 32 Diethyl 5-butoxy-2,3-diphenylterepthalate 111e .................................................... 32 General Procedure for the Synthesis of Diethyl 5-Alkoxy-1,4-di(hydroxymethyl)-3,4- diphenylbenzene 112 .............................................................................................. 33 5-Methoxy-1,4-di(hydroxymethyl)-3,4-diphenylbenzene 112a ............................. 33 5-Hydroxy-1,4-di(hydroxymethyl)-3,4-diphenylbenzene 112b from 111b ........... 33 5-Benzyloxy-1,4-di(hydroxymethyl)-3,4-diphenylbenzene 112c .......................... 34 5-Hydroxy-1,4-di(hydroxymethyl)-3,4-diphenylbenzene 112b from 111d ........... 34 5-Hydroxy-1,4-di(hydroxymethyl)-3,4-diphenylbenzene 112b from 94 ............... 35 General Procedure for the Synthesis of Diethyl 5-Alkoxy-1,4-di(chloromethyl)-3,4- diphenylbenzene 113 .............................................................................................. 35 5-Methoxy-1,4-di(chloromethyl)-3,4-diphenylbenzene 113a ................................ 36 5-Benzyloxy-1,4-di(chloromethyl)-3,4-diphenylbenzene 113c .............................. 36 Poly(5-methoxy-1,4-phenylene vinylene) 114a ..................................................... 36 v TABLE OF CONTENTS (CONTINUED) Page RESULTS AND DISCUSSION ................................................................................... 38 2,5-Di(ethoxycarbonyl)-3,4-diphenylcyclopentadienone 91 ........................................ 38 Diethyl 5-([N-methyliminodiacetato-O,O’,N]borane)- 2,3-diphenylterephthalate 108 ....................................................................................... 40 Synthesis of Hydroxy Phenylated Terephthalate .......................................................... 43 Alkylation of Hydroxy Phenylated Terephthalate ........................................................ 53 Reduction of Alkoxy Phenylated Terephthalate ........................................................... 64 Chlorination of Alkoxy Phenylated Terephthalate ....................................................... 71 Poly(5-methoxy-1,4-phenylene vinylene) .................................................................... 74 CONCLUSIONS ........................................................................................................... 76 FUTURE WORK .......................................................................................................... 77 REFERENCES ............................................................................................................ 103 VITAE .......................................................................................................................... 105 vi LIST OF FIGURES Figure Page 1. Expanded aliphatic region of the NMR spectrum of 91 ..................................... 39 2. Found 1H NMR and 13C NMR Shifts of 91 ........................................................ 39 3. Expanded aliphatic region of the NMR spectrum of 108 ................................... 41 4. Found 1H NMR and 13C NMR Shifts of 108 .....................................................
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