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The Synthesis and Characterization of Novel Pentafluorosulfanyl-Containing Heterocycles and Pentafluorosulfanyldifluoromethane

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The Synthesis and Characterization of Novel Pentafluorosulfanyl-Containing Heterocycles and Pentafluorosulfanyldifluoromethane Clemson University TigerPrints All Dissertations Dissertations May 2019 The yS nthesis and Characterization of Novel Pentafluorosulfanyl-Containing Heterocycles and Pentafluorosulfanyldifluoromethane Steven Paul Belina Clemson University, [email protected] Follow this and additional works at: https://tigerprints.clemson.edu/all_dissertations Recommended Citation Belina, Steven Paul, "The yS nthesis and Characterization of Novel Pentafluorosulfanyl-Containing Heterocycles and Pentafluorosulfanyldifluoromethane" (2019). All Dissertations. 2373. https://tigerprints.clemson.edu/all_dissertations/2373 This Dissertation is brought to you for free and open access by the Dissertations at TigerPrints. It has been accepted for inclusion in All Dissertations by an authorized administrator of TigerPrints. For more information, please contact [email protected]. THE SYNTHESIS AND CHARACTERIZATION OF NOVEL PENTAFLUOROSULFANYL-CONTAINING HETEROCYCLES AND PENTAFLUOROSULFANYLDIFLUOROMETHANE A Dissertation Presented to the Graduate School of Clemson University In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Chemistry by Steven Paul Belina May 2019 Accepted by Joseph S. Thrasher, Ph.D., Committee Chair Julia L. Brumaghim, Ph.D. R. Karl Dieter, Ph.D. Joseph W. Kolis, Ph.D. Title Page ABSTRACT Beginning in the early 1960s, scientists began to experiment with the pentafluorosulfanyl moiety. The unique properties of the functional group has attracted interest among fluorine chemists and more recently even organic chemists. These properties include high group electronegativity, high steric bulk, high lipophilicity, a highly electron withdrawing nature, and a square pyramidal geometry. However, the development and deployment of the pentafluorosulfanyl functional group has been significantly slowed. The main cause for the slow development is a lack of easily available reagents to synthesize pentafluorosulfanyl-containing compounds. Historically, the primary reagents used for synthesizing pentafluorosulfanyl-containing compounds were SF5Cl and SF5Br. These two compounds are difficult to synthesize, cost prohibitive, and difficult to utilize without a vacuum line. With the development of a convenient, cost- effective synthesis of phenylsulfur pentafluorides, the presence of pentafluorosulfanyl in synthetic chemistry has been increasing. Starting from SF5N=CCl2, a number of five-membered heterocycles have been synthesized. Starting from 1,2-substituted binucleophiles, several classes of heterocycles have been formed, including SF5N= substituted carbonates, a pentafluorosulfanylimino- substituted benzothiazolinone, and a pentafluorosulfanylimino-substituted benzoxazolinone. Another aspect of this work depends on a reagent that has recently been synthesized in a reliable, safe and scalable method, namely pentafluorosulfanyldifluoroacetic acid. Pentafluorosulfanyldifluoroacetic acid can be converted to the corresponding acyl chloride by reaction with PCl5, and subsequently added to the amino group of various 2-amino benzamides. The newly formed 2- pentafluorosulfanyldifluoroacetamido benzamides can then be cyclized to quinazolinones by a dehydration in glacial acetic acid. From SF5CF2I, pentafluorosulfanyldifluoromethane has been synthesized by two reductive methods. The first method utilized by tri-n-butyl tin hydride to produce SF5CF2H, at 37% yield. The second method utilized a solution of triethylborane in hexanes, with had a yield of 49% of SF5CF2H. Pentafluorosulfanyldifluoromethane was first reported in 1950, though the primary evidence of this discovery was provided in the form of an empirical formula, derived from elemental analysis. Here, a more thorough spectroscopic analysis of the compound is presented, including IR, NMR and Raman spectroscopy. ii DEDICATION Thank you to my parents, Carol and Gary Belina for their support throughout my research. Thank you to my wife, Xiaolin. Her constant encouragement and kindness are a source of inspiration to me. I would like to dedicate this dissertation to her. iii ACKNOWLEDGEMENTS This work was made possible with financial support from the National Science Foundation. I would like to acknowledge Dr. Charles Bauknight for his assistance in the lab. I am indebted to Dr. Andrej Matsnev for his helpful discussions, his help with techniques, and his willingness to assist with my projects. I would also like to acknowledge Dr. Colin McMillen for his help with respect to X-ray diffraction studies of my compounds. I would like to acknowledge Prof. George Chumanov for his help with the Raman spectrum of SF5CF2H. I would like to thank Dr. Christian Mück-Lichtenfeld for providing a detailed computational study of SF5CF2H. I would like to acknowledge Dr. Steven Creager for his generous allowance of the use of his lab space. For their collaboration and hospitality, I would like to acknowledge Dr. Anna-Lena Drier, Dr. Piotr Dudziński, and Prof. Günter Haufe. I would like to acknowledge my committee members, Prof. Julia Brumaghim, for her insight and willingness to assist me, Prof. Joseph Kolis, for his enthusiasm and ability to inspire a passion in me for inorganic chemistry, and Prof. Karl Dieter, for his commitment to help me improve my talents in chemistry. I would like to acknowledge my advisor, Prof. Joseph Thrasher. His guidance has been invaluable throughout the course of my studies at Clemson University. Finally, I would like to acknowledge my wife, Dr. Xiaolin Liu. As a colleague, she has always pushed me to improve and pursue my goals. Her consultations proved to be invaluable during my research. iv TABLE OF CONTENTS ABSTRACT ............................................................................................................................................ ii DEDICATION ........................................................................................................................................ iii ACKNOWLEDGEMENTS .................................................................................................................... iv TABLE OF CONTENTS ........................................................................................................................ v LIST OF TABLES ............................................................................................................................... viii LIST OF FIGURES ............................................................................................................................... ix LIST OF SCHEMES .............................................................................................................................. x CHAPTER ONE ..................................................................................................................................... 1 1.1 Introduction .................................................................................................................. 1 1.2 Thesis ........................................................................................................................... 24 1.3 References .................................................................................................................. 24 CHAPTER TWO .................................................................................................................................. 31 SYNTHESIS OF SF5NC< HETEROCYCLIC COMPOUNDS .......................................................... 31 2.1 Introduction ................................................................................................................ 31 2.2 Experimental .............................................................................................................. 38 2.2.1 Reagents and synthetic equipment .......................................................... 38 21 2.2.2 Synthesis of sulfur chloride pentafluoride (SF5Cl) ............................... 38 19 2.2.3 Synthesis of pentafluorosulfanyldichloroimine (SF5NCCl2) ................ 40 2.2.4 Synthesis of N-pentafluorosulfanyl-1,3-benzothiazol-2-imine (Compound 1) .............................................................................................. 40 v 2.2.5 Synthesis of N-pentafluorosulfanyl-1,3-benzodioxol-2-imine (Compound 2) .............................................................................................. 41 2.2.6 Synthesis of N-pentafluorosulfanyl-1,3-benzoxazol-2-imine (Compound 3) .................................................................................................................... 42 2.2.7 Synthesis of 4,4,5,5-tetramethyl-N-pentafluorosulfanyl-1,3-dioxolan-2- imine (Compound 4) ................................................................................... 43 2.2.8 Synthesis of N-pentafluorosulfanyl-1,3-dioxolan-2-imine (Compound 5) 44 2.2.9 Attempted preparation of (Z)-3-butyl-N- (pentafluorosulfanyl)benzo[d]thiazol-2(3H)-imine................................... 45 2.2.10 Attempted preparation of 2-hydroxyphenyl N’-pentafluorosulfanyl-N- dodecylcarbamimidate ................................................................................ 46 2.3 Results and Discussion .......................................................................................... 46 2.4 Conclusions ............................................................................................................... 60 2.5 References .................................................................................................................. 61 CHAPTER THREE .............................................................................................................................
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