University of Montana ScholarWorks at University of Montana Graduate Student Theses, Dissertations, & Professional Papers Graduate School 1982 Synthetic study of levoglucosenone Maria G. Essig The University of Montana Follow this and additional works at: https://scholarworks.umt.edu/etd Let us know how access to this document benefits ou.y Recommended Citation Essig, Maria G., "Synthetic study of levoglucosenone" (1982). Graduate Student Theses, Dissertations, & Professional Papers. 8143. https://scholarworks.umt.edu/etd/8143 This Thesis is brought to you for free and open access by the Graduate School at ScholarWorks at University of Montana. It has been accepted for inclusion in Graduate Student Theses, Dissertations, & Professional Papers by an authorized administrator of ScholarWorks at University of Montana. For more information, please contact [email protected]. COPYRIGHT ACT OF 1976 Th is is an unpublished m a nu sc ript in w hich c o pyr ig h t sub ­ s i s t s . Any further r e p r in t in g of it s contents must be approved BY th e a u th o r . MANSFIELD L ibrary U n iv e r s it y of Montana nATpi 19R2 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. A SYNTHETIC STUDY OF LEVOGLUCOSENONE by Maria G. M. Essig B.S., University of California, Irvine, 1979 Presented in partial fulfillm ent of the requirements for the degree of Master of Science UNIVERSITY OF MONTANA 1982 Approved by: Chairman of Examiners DecTn, Graduate Schïïb F -^ / / - ^ ^ Date Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. UMl Number: EP38944 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. UMI* Dissertation PuWistwng UMI EP38944 Published by ProQuest LLC (2013). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code P ro .Q ^s t ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 4 8 1 0 6 -1 3 4 6 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Essig, Maria G. M., M. S., 1982 Chemistry A Synthetic Study of Levoglucosenone (42 pp.) Director: Fred Shafizadeh The synthetic capabilities of 1,6-anhydro-3,4-dideox.y-B-D-glycero- hex-3-enopyranos-2-ulose (levoglucosenone) have been investigated through a variety of reactions. Interesting polycyclic derivatives have been synthesized through 4+2 cycloadditions as well as the oxidation of these cycloaddition products with a variety of oxi­ dants. Long-chain (C^ q to C^o) Grignard reagents have added to levoglucosenone, at both the C-2 and the C-4 positions, yielding compounds which have the potential to be nonionic detergents. The reactions of amines with levoglucosenone producing addition products in low yields, have also been investigated. Results from photo­ induced reactions involving levoglucosenone are also discussed. The reactions outlined demonstrate the stereoselectivity of attack which is induced by the 1 ,6 -anhydro bridge of levogluco­ senone in all but a few cases. This allows the synthesis of many products without the production of isomers in most instances. 11 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. To niy parents, Dolores and Alvin, and my husband, Don m Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Acknowledgments I would like to express my gratitude to the National Science Foundation for the support of this work, and to my advisor. Dr. Fred Shafizadeh, for his encouragement. Thanks are also due to Dr. Edward Waali for his many helpful discussions, Thomas T. Stevenson for his advice and the wry humor which made the rough spots easier, and Marian Manthie for the patient typing and re-typing of manuscripts. IV Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS ABSTRACT.............................................................................................................................ii ACKNOWLEDGMENTS.............................................. iv LIST OF TABLES AND FIGURES....................................................................................... vi CHAPTER I. Introduction................................................... 1 II. History ................................................................................................................3 I I I . Results and Discussion .................................................................................. 5 IV. Experimental.....................................................................................................27 BIBLIOGRAPHY ................................................................................................................. 41 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF TABLES AND FIGURES TABLE I. assignments for compounds 5 through 12 . 7 TABLE I I . Selected coupling constants for compounds 5 through 1 2................................................................................ ~........................... n 1 TABLE I I I . H-n.m.r. assignments for the barnched-chain products 13 through 1 7 .................................................................... 19 TABLE IV. Selected ^H-n.m.r. shifts 6( , p.p.m.) and coupling constants (Hz) for compounds 18 through 2 0 .........................23 FIGURE I. Direction of attack on levoglucosenone .............................. 6 FIGURE I I . Norbornyl nomenclature ............................................................... 8 FIGURE I I I . A computer drawing of the epoxide8 from crystallographic data showing thermal motion of the atoms ......................................................................................... 10 VI Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CHAPTER I Introduction Carbohydrates are of great interest, both practically and theoretically. They have added to the chemist's knowledge of stereo­ chemistry and provided an important example of the van't Hoff - Le Bel theory of the tetrahedral nature of carbon valencies.^ They are among the most abundant of natural products, are easily isolated, and have unique biological activity. However, the u tilizatio n of carbohy­ drates as synthetic starting materials has several disadvantages. The variety of functionality in carbohydrates is generally limited to hydroxyl and carbonyl groups. Having a number of similar hydroxyl groups makes specific attack at any one position difficult. The traditional method of utilizing carbohydrates as synthetic intermedi­ ates involves the selective protection of hydroxyl groups, or dehydra­ tion and anhydro ring formation, before addition of new groups to the skeleton of the sugar. These disadvantages can be overcome by u tilizin g a carbohydrate derivative which contains more versatile functionality but still maintains a link with biological systems. One such derivative is levoglucosenone (1, 1,6-anhydro-3,4-dideoxy-B-D-qlycero-hex-3- enopyranos-2 -ulose), which is easily isolated from the tar fraction Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. after the pyrolysis of cellulosic material (such as newspaper) pre­ treated with phosphoric acid. Levoglucosenone is an interesting molecule with numerous synthetic possibilities. Compounds similar to levoglucosenone have been utilized as starting materials in the 2 3 4 synthesis of antibiotics ’ and insect pheromones, and the levogluco­ senone structural unit has been found in natural products isolated from 5 the plant Zinnia peruviana. Some of the synthetic utility of levoglu- f\ 7 cosenone has been studied such as reductions and oxidations, * 4+2 cycloadditions,^ Michael additions,^ oligomerizations,^^ and other 6 7 11 reactions. * * The results of these reactions have indicated further research would be fru itfu l. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CHAPTER I I History In an effo rt to gain knowledge about the fireproofing of flammable materials, find new sources of useful chemicals, and elucidate the mechanism by which cellulose thermally degrades, the products of cellulose pyrolysis have been the subject of intensive investigation. Early studies of cellulose pyrolysis were concerned with the relative proportions of the gas, ta r, and char fractions after pyrolysis. High tar yields became associated with greater flammability characteristics therefore treating cellulosic materials with fire retardants resulted in reduced tar yields. In 1918, a 1 2 major constituent of tar was isolated and named levoglucosan which 13 in 1929 was identified as 1,6-anhydro-g-D-glucopyranose, 2. In many studies since levoglucosan was identified, high yields of levoglucosan became equated with high tar yields, and thus, high flammability characteristics since the first and rate-determining