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Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1975 Reactive Polymers in Organic Synthesis; Ortho- Benzoquinone and Ortho-Dihydroxyphenyl Derived Polymer Reagents. Dwight Crawford Kaufman Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Kaufman, Dwight Crawford, "Reactive Polymers in Organic Synthesis; Ortho-Benzoquinone and Ortho-Dihydroxyphenyl Derived Polymer Reagents." (1975). LSU Historical Dissertations and Theses. 2838. https://digitalcommons.lsu.edu/gradschool_disstheses/2838 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. 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Xerox University Microfilms 300 North Zeeb Road Ann Arbor, Michigan 48106 I I 76-152 KAUFMAN, Dwight Crawford, 1945- REACTIVE POLYMERS IN ORGANIC SYNTHESIS: ' o-BENZOQUINONE- AND 6-DIHYDRQXYPHENYL- DERTVED POLYMER REAGENTS. The Louisiana State University and Agriculture and Mechanical College, Ph.D., 1975 Chemistry, organic Xerox University Microfilms, Ann Arbor, Michigan 48106 THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED. REACTIVE POLYMERS IN ORGANIC SYNTHESIS; o-BENZOQUINONE- AND o-DIHYDROXYPHENYL-DERIVED POLYMER REAGENTS A DISSERTATION Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy xn The Department of Chemistry by Dwight Crawford Kaufman B.S., Ouachita University, 1967 August, 1975 "You've been taken on as Land-Surveyor, as you say, but, unfortunately, we have no need of a land-surveyor. There wouldn't be the least use for one here "But how is that possible?" cried K. "Surely I haven't made this endless journey just to be sent back again!" -- Kafka The Castle ACKNOWLEDGEMENTS I gratefully acknowledge Professor William H. Daly for his conceiving of the main idea upon which the research herein described is based, for offering to me the opportunity to pursue the research, and for his assistance during the pursuit. I wish to thank Professor Kendall N. Houk for providing me with employment during the months preceding the completion of this dissertation, for stimulating my interest and augmenting my competence in a field of research with which I had little previous familiarity, and for being so remarkably patient with me through a difficult period. The financial assistance for the preparation of this Disserta­ tion by the Dr. Charles E. Coates Memorial Fund of the LSU Foundation, donated by George H. Coates is gratefully acknowledged. To my friend, Dr. Angelo Russo, I express my sincere gratitude for his invaluable assistance and suggestions, for his continual intellectual stimulation, and for many other things, too profound and personal adequately to be expressed. To M.L.R., to L.B.E., to P.N.E., to J.B., to J.H.R.S., R.J.V.— thanks. To Deborah, thanks — and apologies. iii TABLE OF CONTENTS PAGE ACKNOWLEDGEMENT....................................... ii LIST OF T A B L E S ....................... xii LIST OF SCHEMES........................................ xiii ABSTRACT................................................. xvi PART I REACTIVE POLYMERS IN ORGANIC SYNTHESIS........ 1 I « INTRODUCTION oeeseaaoBaevtsessa 2 II. REACTIVE SUBSTRATES ^ A. Peptide Syntheses ........................ ^ B. Oligonucleotide Synthesis ................ 10 C. The "Infinite Dilution" Effect ............ 11 1. Peptide Cyclization................. 12 2. Ester Condensation .................... 15 3. Polymeric Blocking G r o u p s ............ 21 III. ACTIVE PARTICIPANTS......................... 25 A. Polymer Catalysts........................ 26 1. Ion Exchange R e s i n s ........... 26 2. Transition Metal Catalysts ............ 29 3. Polymer-Bound E n z y m e s ................ 32 if. Enzyme Analogues..................... 33 B. Polymer Reagents ........................ 36 1. Polymeric Oxidizing and Dehydrating Reagents ............. ........ yj iv TABLE OF CONTENTS continued PAGE 2 . Polymeric Acylating Reagents............ k6 3. Polymeric Ylide Reagents . .............k-9 Peracid Resins ............. ............5 I4- IV. DESIGN OF REACTIVE POLYMERS..................... 56 V. THE FUTURE OF REACTIVE POLYMERS IN ORGANIC SYNTHESIS...................... .............. 58 REFERENCES................................... 60 PART II o-BENZOQUINONE- and o-DIHYDROXYPHENYL-DERIVED POLYMER REAGENTS ........................69 I. INTRODUCTION................................... 70 A. Synthetic Reagents Derived from Catechol . 70 1. Catechol Dichlordmethylene Ether .... 72 2 . o-Phenylene Phosphorochloridite .... 7 3 3. Catechyl Phosphorous Trihalide ........ 76 4 . o-Phenylene Phosphorochloridate ........ 7 7 5. Catecholborane ......... ....... 8l B. Synthetic Reagent Derived from o-Benzoquinone............................. 8lt- C. Precedents for Polymeric Catechols ........ 88 D. Background and Objectives . .............. 92 II. RESULTS AND DISCUSSION......................... 95 A. Synthesis of Catechol Derivatives for Immobilization of Polymer.................... 95 1. Syntheses of Vinyl Monomers..............9T v TABLE OF CONTENTS continued PAGE a. Isopropylidene-Blocked 3“Vinyl-5- £-butylcatechol .................97 b. U - Vinylcatecho1 ..... ........... 101 2. Syntheses of Nucleophilic Catechol Derivatives ..................... 106 B. Preparation and Modifications of Polymer- Immobilized Catechols..................... .110 1. Polymerization and Subsequent Reactions of 6 -t■-Butyl-2,2-dimethyl-k-vinyl-1, 3 - benzodioxole .......... ............ 110 2. Preparation of Catechol Reagents by Nucleophilic.Substitution .............. 116 3. Preparation and Use of Immobilized o-Phenylene Phosphorochloridate ........ 125 C. Summary .......................128 III. EXPERIMENTAL ...... - . ............... 129 A. General Information ...................129 B. Monomer Syntheses ........................ 131 1. Attempted Preparation of 1,2-bis- Methoxymethyl Ether of 4-Jt-Butylcatechol. 131 2. Preparation of 5 “Butyl-2,2-dimethyl- / 1,3 -benzodioxole....................... 132 3 . Attempted Preparation of 6 -t-Butyl-2,2- d imethy 1 -if -hydroxy ethyl -1,3 -benzod ioxo le by Lithiation of 5-t-Butyl-2,2-dimethyl- vi TABLE OF CONTENTS continued PAGE 3. 1,3-benzodioxole ...................... 134 4. Preparation of 4-Bromo-6-t-butyl- 2.2-dimethyl-1,3-benzodioxole ........ 135 5 . (a) Preparation of 6 -t-Butyl-2,2- dimethyl-4-(1-hydroxyethy1)-1,3 - benzodioxole . ..................... 136 (b) Preparation and Use in Grignard Synthesis of Highly Active Magnesium . 138 6 . Preparation of 6-£-Butyl-2,2-dimethyl- 4-hydroxymethyl-l,3“benzodioxole.... 138 7 . Preparation of 6 -t-Butyl-2,2-dimethyl- 4-(2 -hydroxyethyl)-l,3 “benzodioxole . 139 8 . Preparation of 6-t-Butyl-2,2-dimethyl- 4-vinyl-l,3 -benzodioxole . .......... ll|-0 9. Preparation of 6 -t-Butyl-2,2-dimethyl- li-- (2 -£-to luenes ul f onoxye t hy 1 ) -1,3- benzodioxole '............... l4l 10. Preparation of 6 -t-Butyl-4-(2-chloro- ethyl)-2 ,2 -dimethyl-l,3 -benzodioxole . 142 11. (a) Attempted Preparation of 6 -t^-Butyl- 2.2-dimethyl-4-(2-mercaptoethyl)-l,3- benzodioxole via the Thiouronium Salt; Preparation of 4,4'-[Thiobis(2-ethyl)- di-(6-_t-butyl-2,2-dimethyl-l,3- benzodioxole)] . 145 vii TABLE OF CONTENTS continued PAGE 11. (b) Preparation

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