Structure Elucidation of Secondary Metabolites from Rudbeckia Species by Spectroscopic Techniques and Review of Sesquiterpene Lactones
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Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1989 Structure Elucidation of Secondary Metabolites From Rudbeckia Species by Spectroscopic Techniques and Review of Sesquiterpene Lactones. Marta Vasquez Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Vasquez, Marta, "Structure Elucidation of Secondary Metabolites From Rudbeckia Species by Spectroscopic Techniques and Review of Sesquiterpene Lactones." (1989). LSU Historical Dissertations and Theses. 4815. https://digitalcommons.lsu.edu/gradschool_disstheses/4815 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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Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Order Number 9017299 Structure elucidation of secondary metabolites fromRudbeckia species by spectroscopic techniques and review of sesquiterpene lactones Vasquez, Marta, Ph.D. The Louisiana State University and Agricultural and Mechanical Col., 1989 Copyright ©1990 by Vasquez, Marta. All rights reserved. U M ’I 300 N. Zeeb Rd. Ann Arbor, MI 48106 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. STRUCTURE ELUCIDATION OF SECONDARY METABOLITES FROM RUDBECKIA SPECIES BY SPECTROSCOPIC TECHNIQUES AND REVIEW OF SESQUITERPENE LACTONES 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 The Department of Chemistry by Marta Vasquez Universidad de Antioquia, Colombia, 1971 . , Universidad del Valle, Colombia, 1981 August 1989 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. To my family members for believing in the worth of this project Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGMENTS There are a number of people who make an effort such as this possible. I wish I could thank all who helped not only those whose suggestions aided the research, but also those who facilitated the writing. Included in this group are: Dr. Nikolaus H. Fischer who gave me encouragement and help when it seemed as if I had reached an insurmountable obstacle, Dr. Leovigildo Quijano (Professor Instituto de Quimica, Universidad Nacional de Mexico, Mexico) who was helpful in discussions about different aspects of structure elucidation, his help will be always remembered and appreciated. Dr. Francisco A. Macias, Associate Professor at the Universidad de Cadiz, Spain, who during his stay at LSU introduced me to the fascination of the sesquiterpene lactone world, without his enthusiasm and help, I might have never finished this project; Dr. Lowell E. Urbatsch and Patricia B. Cox to whom sincere thanks are expressed tofor their aid in plant collection and identification and for the discussions related to the systematics of the genus Rudbeckia; and my husband, Robert Zinn, to whom I am grateful for improving the manuscript as it went through revisions and for lending computers which made it easier for this dissertation to be I would like to extend my gratitude to Dr. Luis E. Vidaurreta and Dr. Robert V. Nauman for their priceless help and encouragement. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. I wish to thank Dr. Frank Fronczek for the X-ray crystallographic data included in this dissertation. Although I obtained most of the spectroscopic data in this dissertation, some infrared spectra were obtained by Rafael Cueto. To him, I give my thanks. My thanks too go to Marcus Nauman who helped with the NMR instrument and to Luz Barona and Henry Hurtado who helped with the drawings. Thanks especially are given to my fellow graduate students, present and former for their help and advice. Their survival of the ordeal gave me hope. To each of them and others I am grateful. To these and many other friends, I express my warmest gratitude. They have all enabled me to do the things I wanted and needed to do. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. This dissertation consists of seven chapters, five of which are manuscripts that have been published, accepted or submitted for publication, to various journals. The author of this dissertation, is also the primary author of the manuscripts, and has received permission to include the materials in this dissertation. Chapters 1-3 are phytochemical investigations, which concentrate on spectral interpretation. These chapters were written following the recommended style for the journal Phytochemistry. Chapters 4 and 5 concentrate on crystal structures which were written in the style of Acta Crystallographica. Phytochemistry and Acta Crystallographica are considered leading international journals in their fields. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CONTENTS OF PART A ACKNOWLEDGEMENTS........................................... m PREFACE.................................................... V LIST OF TABLES............................................. viii LIST OF FIGURES............................................ x ABBREVIATIONS.............................................. xvi DISSERTATION ABSTRACT..................................... xviii GENERAL INTRODUCTION....................................... 1 Chapter 1. SESQUITERPENE LACTONES FROM RUDBECKIA GRANDIFLORA... 7 1.1. Abstract..................................... 8 1.2. Introduction................................. 8 1.3. Results and Discussion....................... 9 1.4. Experimental................................. 14 References................................... 17 Chapter 2. SESQUITERPENE LACTONES AND LIGNANES FROM RUDBECKIA SPECIES AND THE MOLECULAR STRUCTURES OF GAZANIOLIDE AND TAMAULIPIN A ANGELATE........................ 51 2.1. Abstract..................................... 52 2.2 Introduction................................. 53 2. 3 Results and Discussion....................... 54 2.4 Experimental................................. 59 References................................... 64 Chapter 3. SESQUITERPENE LACTONES FROM RUDBECKIA MOLLIS...... 90 3.1. Abstract..................................... 91 3.2. Introduction................................. 91 3.3. Results and Discussion....................... 92 3.4 Experimental................................. 99 References................................... 103 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Chapter 4. STRUCTURE OF THE LIGNANE (+)-PINGRESINOL DIMETHYL ETHER........................................... 126 4. 1 Abstract..................................... 127 4.2 Experimental................................. 127 4. 3 Related Literature........................... 129 References................................... 130 Chapter 5. STRUCTURES OF THREE SESQUITERPENE y-LACTONES FROM RUDBECKIA MOLLIS................................. 136 5.1. Abstract..................................... 137 5.2. Introduction................................. 138 5.3. Experimental................................. 138 5.4.