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Information to Users INFORMATION TO USERS The most advanced technology has been used to photograph and reproduce this manuscript from the microfilm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be fi’om any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g.. maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand corner and continuing from left to right in equal sections with small overlaps. Each original is also photographed in one exposure and is included in reduced form at the back of the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. UMI University Microfilms International A Bell & Howell Information Company 300 North Zeeb Road, Ann Arbor, Ml 48106-1346 USA 313/761-4700 800/521-0600 Order Number 9111814 Synthesis and chemistry of phenyl(tTimethylstannyl)diazomethane and lithium phenyldiazomethane Wheeler, Michael Thurman, Ph.D. The Ohio State University, 1990 UMI 300 N. Zeeb Rd. Ann Arbor, MI 48106 SYNTHESIS AND CHEMISTRY OF PHENYL(TRIMETHYLSTANNYL)DIAZOMETHANE AND LITHIUM PHENYLDIAZOMETHANE DISSERTATION Presented in Partial Fulfillment of the Requirem ents for the Degree of Doctor of Philosophy in the Graduate School of the Ohio State University By Michael T. Wheeler, M.S. The Ohio State University 1990 Dissertation Committee: Approved by Dr. Harold Shechter Dr. Anthony Czarnik Dr. Gideon Fraenkel Adviser Department of Chemistry To My Family ii ACKNOWLEDGMENTS I would sincerely like to thank Professor Harold Shechter for his many helpful suggestions and discussions during the course of this research endeavor. I will always remember his absolute dedication to being a Teacher both in the classroom and in the laboratory, I am grateful for having had the opportunity to learn research principles under his direction. Also I would like to thank all of the members of the Shechter Research Group for all the interesting discussions that we have had over the years. I would like to extend my appreciation to the Ohio State University and the National Science Foundation for their financial support. Also I would like to thank Wiley Organics of Cochocton, Ohio for their kind donation of several research samples. ill VITA 1981 ........................................................................................... B.S., Ohio State University, The Ohio State University, Columbus, Ohio 1981 -1984 .................................................................................M.S., University of Toledo, Toledo, Ohio 1984-1987 Teaching Associate,Department of Chemistry, The Ohio State University, Columbus, Ohio 1987-1990 ............................................. Research Associate, Department of Chemistry The Ohio State University, Columbus, Ohio FIELD OF STUDY Major Field: Chemistry iv TABLE OF CONTENTS DEDICATION.......................................................................................................................... II ACKNOWLEDGMENTS...................................................................................................... ill VITA.........................................................................................................................................Iv LIST OF FIGURES...............................................................................................................vll LIST OF TABLES.................................................................................................................. xl STATEMENT OF PROBLEM................................................................................... 1 HISTORICAL Introduction................................................................................................•.................2 Synthesis of a-Metalloldo and a-Metallo DIazo Compounds .........................3 Chemistry of a-Metalloldo and a-Metallo DIazo Com pounds......................13 RESULTS AND DISCUSSION Introduction............................................................................................................... 24 Synthesis of Phenyl(trimethylstannyl)dlazomethane (70) ............................ 24 Cycloaddition Reactions of 70 ...............................................................................28 Bromlnatlon of 70.....................................................................................................36 Photolysis and Thermolysis of 70 ..........................................................................38 Rhodlum(ll) Acetate Catalyzed Decomposition Reactions of 70 ..............44 The Relative Reactivities of Triethylsllane and Ethyl Vinyl Ether Towards 70/Rhodium(ll) Acetate ..........................................................................61 Synthesis and Chemistry of Lithium Phenyldiazomethane (72) ................62 SUMMARY...........................................................................................................................75 EXPERIMENTAL..................................................................................... 78 APPENDICES A. 1H-NMR and '•^C-NMR Spectra for New Compounds .......................... 107 B. Alternative Mechanisms for Diastereoseiectivity of Metai Catalyzed Decompositions of Diazo Compounds ....................................144 REFERENCES..................................................................................................................152 vi LIST OF FIGURES FIGURE PAGE 1 Carbon-tin (p-d)jc Back-bonding In 7 0 .......................................................28 2 Nucleophilic Diazo Carbon Attacks ^-Position of Mono-acceptor-substitued Alkene...........................................................31 3 Possible Geometric Isomers of Azine 118 ............................................40 4 Structure of Rhodium(ll) Acetate............................................................... 45 5 Rhodium(ll) Acetate Ylide ...........................................................................45 6 Insertion of Carbene 71 into a Si-H B o n d ............................................. 50 7 Insertion of Unsaturated Carbene into a Si-H Bond ........................... 50 8 Possible Geometric Isomers of Azines 173 and 174 ......................... 73 9 250 MHz 1 H-NMR of Phenyl(trimethylstannyl)diazo- methane (70) ................................................................................................108 10 63 MHz 1 3c -NMR of Phenyl(trimethylstannyl)diazo- methane (70) ................................................................................................109 11 250 MHz 1 H-NMR of N,3-Diphenyl-2-pyrazoline-4,5- dicarboximide (83)......................................................................................110 12 63 MHz 1 3C-NMR of N,3-Diphenyl-2-pyrazoline-4,5- dicarboximide (83).........................................................................111 1 3 250 MHz 1 H-NMR of 3-Pyrazoline-5-carbonitrile (87).................. 112 14 63 MHz 13C-NMR of 3-Pyrazoline-5-carbonitrile (87)......................113 1 5 250 MHz 1 H-NMR of 3-Phenyl-1 -(trimethyl- stannyl)-1H-benz[f]indazole-4,9-dione (93)........................................ 114 VÜ 1 6 63 MHz 13C-NMR of 3-Phenyl-1-(trimethyl- stannyl)-1 H-benz[f]in-dazole-4,9-dione (93)............................. .115 17 250 MHz 1 H-NMR of 3-Phenyl-1-trimethylstanny!pyrazole- 4,5-dicarboxylate (101).............................................................. .116 18 63 MHz 13C-NMR of 3-Phenyl-1-trimethylstannylpyrazole- 4,5-dicarboxylate (101).............................................................. 117 19 250 MHz 1 H-NMR of 3,4,5-Triphenylpyrazole (105)................ .118 20 63 MHz I^C-NMR of 3,4,5-Triphenylpyrazole (105)................ ,,.119 21 250 MHz 1 H-NMR of Bis(trimethylstannyl)benzal- azine (118).............................................................................................. .120 22 63 MHz 13C-NMR of Bis(trimethylstannyl)benzal- azine (118)............................................................................... 121 23 250 MHz 1 H-NMR of a-Triethylsiiyl-a-trimethylstannyl- toluene (129)............................................................................ 122 24 250 MHz 13C-NMR of a-Triethylsilyl-a-trimethylstannyl- toluene (129)............................................................................ 123 25 300 MHz 1 H-NMR of a-Triisopropylsilyl-a-trimethyl- stannyltoluene (131)................................................................. 124 26 75 MHz 13C-NMR of a-Tiiisopropylsilyl-a-trimethyl- stannyltoluene (131)................................................................. ...125 27 250 MHz 1 H-NMR of a-Dimethylphenylsilyl-a-trimethyl- stannyitoluene (133)................................................................. 126 28 63 MHz ‘•3H-NMR of a-Dimethylphenylsilyl-a-trimethyl-
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