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Xerox University Microfilms 300 North Zeeb Road Ann Arbor, Michigan 48108 76- 18.059 WEXLER, Allan Jay, 1947- the PHOTOCYCLOADDITION CHEMISTRY of 5-FLUOROURACIL INFORMATION TO USERS This material was produced from a microfilm copy of the original document. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the original submitted. The following explanation of techniques is provided to help you understand markings or patterns which may appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting thru an image and duplicating adjacent pages to insure you complete continuity. 2. When an image on the film is obliterated with a large round black mark, it is an indication that the photographer suspected that the copy may have moved during exposure and thus cause a blurred image. You will find a good image of the page in the adjacent frame. 3. When a map, drawing or chart, etc., was part of the material being photographed the photographer followed a definite method in "sectioning" the material. It is customary to begin photoing at the upper left hand corner of a large sheet and to continue photoing from left to right in equal sections with a small overlap. If necessary, sectioning is continued again — beginning below the first row and continuing on until complete. 4. The majority of users indicate that the textual content is of greatest value, however, a somewhat higher quality reproduction could be made from "photographs" if essential to the understanding of the dissertation. Silver prints of "photographs" may be ordered at additional charge by writing the Order Department, giving the catalog number, title, author and . specific pages you wish reproduced. 5. PLEASE NOTE: Some pages may have indistinct print. Filmed as received. Xerox University Microfilms 300 North Zeeb Road Ann Arbor, Michigan 48108 76- 18.059 WEXLER, Allan Jay, 1947- THE PHOTOCYCLOADDITION CHEMISTRY OF 5-FLUOROURACIL. The Ohio State University, Ph.D., 1976 Chemistry, organic Xerox University Microfiims, Ann Arbor, Michigan 4810 e THE PHOTO CYCLOADDITION CHEMISTRY OF 5-FLUOROURACIL DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University by Allan Jay Wexler, B. S., M. S. ***** The Ohio State University 1 9 7 6 Reading Committee: Approved by John S. Swenton Harold Shechter Gideon Fraenkel )hn S. Swenton, Adviser )epartment of Chemistry This work is dedicated to my parents, Sylvia and Harry Wolf, and to my grandmother and aunt, Ida Kaplowitz and Nettie Kaplowitz. ii A CKNO WLEDGMENTS I want to thank Professor John Swenton for suggesting the study of a very interesting molecule, 5-fluorouracil. More importantly, however, I want to acknowledge him as a friend, whose dedication and intelligence have earned my profound respect. Many thanks go also to Roberta Swenton for her help In preparing this manuscript and her warm hospitality. i l l VITA October 22, 1947 Born - New York City, New York 1 9 6 8......................... B.S. (cum laude) Brooklyn College of The CLCy University of New York 1 9 7 1......................... M.S. The Ohio State University 1 9 7 6......................... Ph.D. The Ohio State University PUBLICATIONS John S. Swenton and Allan Wexler, "A Stereospecific Vinylcyclopropane Rearrangement due to Hindered Rotation in the Biradical, " J. Am. Chem. Soc. 93, 3066 (1971). Allan Wexler, Robert J. Balchunis, and John S. Swenton, "A Photochemical Synthon for the 5-Uracil Carbanion. Application to the Direct Punctionalization of Unprotected Uracils, '* J. Chem. Soc. Chem. Commun. , 601 (1975). Allan Wexler and John S. Swenton, "Fluorine Control of Regioselectivity in Photocycloaddition Reactions. The Direct Functionalization of Uracil via a Novel 1,4 Fragmentation, " J. Am. Chem. Soc. , in press. IV TABLE OF CONTENTS DEDICATION ........................................................... ii ACKNOWLEDGMENTS ........................................................................................ ill VITA ............................................................................................................................. Iv LIST OF TABLES ............................................................................................... vU l LIST OF FIGURES ............................................................................................... ix Chapter I. HISTORICAL ................................................................................................ I Introduction ..................................................... I 5-Substituted Uracils--Occurrence............................................ 2 S y n th e s is ................................................................................................. 4 A New Approach .................................................................................. 6 II. RESULTS AND DISCUSSION ................................................................ 18 Introduction ........................................................................................... 18 Cycloaddition Reactions of Uracil, Thymine, and 6-M ethyluracil .................................................. 20 Demonstration of Cis Ring Fusions in the Cycloadducts ........................................................................ 23 D is c u s s io n.............................................................................................. 26 The Corey-Wagner M echanism ............................................... 27 Trans Ring Fusions........................................................................ 31 Olefinic Products........................................................................... 38 Effect of a Beta Methyl Group .................................................. 43 Effect of an Alpha Methyl G ro u p ............................................ 47 III. PHOTOCYCLOADDITIONS OF 5 - FLUORO UR A CIL- - A NOVEL FLUORINE SUBSTITUENT EFFECT ................... 49 Introduction .............................................................. 49 Results ........................................................................................ 51 Cycloaddition of 5-Fluorouracil to Isobutylene ...... 51 Cycloaddition of 5-FluorouraciI to Methylene Cyclohexane Methylene Cyclopentane Methylene Cycloheptane ^ ..................................................... 54 Photocycloaddition of Propene to 5-Fluorpuracil. .... 55 Cycloaddition of 1 -Methyl Cyclopentene, 6^ and 5-Fluorouracil .................. 59 Enol Acetate Cycloadditions............................................................... 60 Cycloaddition of Cyclohexenyl Acetate, 7^ and 5-Fluorouracil ..................................... 61 Cycloaddition of Cyclopentenyl Acetate, 74, and 5-Fluorouracil ..................................................................... 65 Discussion ..................................... 66 Mechanistic Rationale for Regioselectivity in Enone Cycloadditions. Origin of the Fluorine Substituent E ffe c t.............................................................................. 69 The PMC Approach........................................................................... 70 The Oriented TT Complex.................................................................. 78 The Overall Dipole Mechanism.................................................. 85 The Radical Reversion Mechanism............................................ 86 IV. FRAGMENTATION REACTIONS--RESULTS .................................. 94 Introduction ........................................................................................... 94 The Spectral Properties of U racils............................................... 94 UV .............................................................................................................. 94 IR ............................... : ........................................................................... 96 NMR ........................................................................................................... 97 "CMR ........................................................................................................ 97 An Anticipated Fragmentation Reaction ...................... 99 Synthesis of 5-(Cyclopentano-2-oxo)uracil 105 ................... 99 Synthesis of 5-(Cyclohexano-2 -oxo)uracil 106 ......................... 100 An Unanticipated Fragmentation............................ 102 Synthesis of 5-(2-Methyl-2-propenyl)uracil W 8 ...................102 Synthesis of 5~(I-Cyclohexenylmethyl)uracil 1 1 0 ................104 Synthesis of 5-(l-Cycloheptenylmethyl)uracil 111 ................106 Synthesis of 5-( 1 -Cyclopentenylmethyl)uracil 112 ................106 D is c u s s io n.................................................................................................... 107 Mechanistic Considerations.................. 107 Enol Acetate Cycloadducts .............................................. 107 Cycloadducts of Simple Alkenes . ............................................110 Mechanistic Studies..................................................................................112 vi Experimental......................... 113 General Procedures............................... 113 Photoadditions in Acetone-W ater.................................................. 114 Photoaddilions of 5-Fluorouracll ......................................118
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