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INFORMATION to USERS the Quality of This Reproduction Is INFORMATION TO USERS This manuscript has been reproduced 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 from 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 comer 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 o f 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 A Bell & Howell Information Company 300 North Zeefc Road. Ann Arbor MI 48106-1346 USA 313/761-4700 800/521-0600 PART 1: STUDIES OF SYNTHESES OF MONO- AND DINITROACETYLENES, ACETYLENIC NITRITES AND NITROSOKETENES PART 2: INVESTIGATION OF GENERATION AND THE FATE OF 2- PYRROLYLMETHYLENES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Christopher J. Woltermann The Ohio State University 1996 Dissertation Committee: Approved by Professor Harold Shechter, Adviser Professor David Hart Professor John Swenton Department of Chemistry UMI Number: 9631007 UMI Microform 9631007 Copyright 1996, by UMI Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. UMI 300 North Zeeb Road Ann Arbor, MI 48103 ABSTRACT Nitration of acetylides (I) with various nitrating agents (N 02BF4, N20 5, N20 4> Me3Si0N 02, n-PrON02) typically results in efficient single electron transfer to yield the corresponding acetylene radicals (2). The acetylene radicals (2) couple with the parent acetylides (1) to give butadiynes upon further electron transfer and loss of metal ion or abstract hydrogen from solvents to afford the parent acetylenes. Attempts to trap acetylene radicals 2 with nitrogen dioxide to yield 1-nitroacetylenes (1) are described. Dinitroacetylene (3) is an unknown but potentially important compound because of its expected high energy and density. Attempts at synthesis of dinitroacetylene (3) by dinitration of 1,2-disubstituted acetylenes at various temperatures and with varied nitrating agents have been investigated. Nucleophilic addition-elimination and rearrangement of phenylethynyl(phenyl)iodonium tosylate (4) by nitrite ion does not yield 1- nitroacetylenes but does give phenylethynyl nitrite (5) which tautomerizes to nitroso(phenyl)ketene (6). Ethynyl nitrites are previously unknown and their behavior is investigated. Study of nitrosoketenes proves that they undergo novel intramolecular [2+2] cycloadditions with subsequent loss of carbon dioxide to yield nitriles. Preparation of dinitroacetylene (3) by Retro Diels-Alder reactions was investigated. Temperatures greater than 250 °C are needed for cycloreversion of 9,10- dihydro- 1 l,12-dinitro-9,10-ethenoanthracene(7). At such high temperatures, 3 does not survive but decomposes to nitrogen and carbon dioxide. A study of more electron-rich anthracene adducts for the retro Diels-Alder reaction to give dinitroacetylene (3) at lower temperatures is described. Synthesis of anthracene adducts related to 7 with electron-donating groups in the 9 and 10 positions by reaction of tetranitroethylene with 9,10-disubstituted anthracenes followed by removal of N20 4 was unsuccessful. Oxidations of cyanogen-N,N’-dioxide (10) to nitro(nitroso)acetylene (11) and dinitroacetylene (3) were investigated. Various oxidants (03, bis- (trimethylsilyl)peroxide, KMn04, M n02, Cr03, Ag20, PDC and H20 2) were employed for this study but none were successful. Utilization of the known nitro(trimethylsilyl)acetylene (8) to prepare new 1- nitroacetylenes by substitution of the trimethylsilyl group is discussed. Removal of the trimethylsilyl group by fluoride ion in an attempt to synthesize nitroacetylene anion (9) results in resinous material even when in the presence of excess electrophiles. Electrophilic addition-elimination on 8 with N 02BF4 does not yield dinitroacetylene (3). in Study has been made of the behavior of l-methyl-2-pyrrolylmethyIene (12) at high temperatures (250-350 °C). The sodium salt of l-methyl-2-pyrrolecarboxaldehyde tosylhydrazone (13) was pyrolized to produce [2-(l -methyl)pyrrolyl]diazomethane (14) as an intermediate with subsequent loss of nitrogen to yield l-methyl-2- pyrrolylmethylene (12). Sodium salt 13 was pyrolyzed to determine whether or not 12 would ring open to E/Z-ynenoneimines (15). In all instances, methylene 12 dimerizes to E/Z-l,2-di(l-methyl-2-methylpyrrolyl)ethylenes (16) and/or reacts with 14 to yield bis-(l-methylpyrrolyl)ketazine (17). 2-Pyrrolylmethylene (18) does not form its dimer but gives a high molecular weight compound which may result from polymerization of cyclopentadienoneimine (19) or 2-methylene-2H-pyrrole (20). IV Dedicated to my wife and daughter v ACKNOWLEDGMENTS I wish to thank those whose friendship and support made the Ph.D. program at Ohio State enjoyable; especially Paul Boxrud, Peter Dalidowitz, Dan Repicz, Tony Skufca, Eric Vendel and Michael Waterman. I would also like to thank those who helped me to become oriented when first joining the Shechter group: Nash Mathur, Larry Yet and Stephan Klump, Professor Shechter has been particularly helpful to me as a graduate student. He has taught me much about chemistry, writing and public speaking. I have truly enjoyed the many conversations we have shared. I would not have been able to complete the Ph.D. program without the support from my parents and especially from my wife, Kathy, and daughter, Angela. VI VITA September 24, 1968 ......................................................................... Bom - Cincinnati, Ohio 1990........................................................................B.S. Chemistry - University of Dayton 1988-1990 Production Chemist - Exciton Inc. 1990-1993.............................. Graduate Teaching Associate, The Ohio State University 1993-1996................................................ Research Associate, The Ohio State University FIELD OF STUDY Major Field; Chemistry Studies in Organic Chemistry TABLE OF CONTENTS Abstract............................................................................................................................................. ii Dedication ..........................................................................................................................................v Acknowledgments .......................................................................................................................... vi Vita...................................................................................................................................................vii List of Figures ..................................................................................................................................x PART 1 Statement of Problem ......................................................................................................1 Chapters: 1. Historical Information ........................................................................................................4 Preparation of 1-Nitroacetylenes ..................................................................... 4 Reactions of 1-Nitroacetylenes .....................................................................13 2, Results and Discussion ...................................................................................................18 Introduction .......................................................................................................... 18 Nitration of Acetylides .................................................................................... 19 Nucleophilic Addition-Elimination ...............................................................40 Retro Diels-Alder Reactions ..........................................................................51 Oxidation of Cyanogen-N,N'-dioxide ......................................................... 58 Reactions of Nitro(trimethylsi!yl)acetylene ................................................ 60 Summary: Part 1.................................................................................................63 3. Experimental Section .......................................................................................................70 PART 2 Statement of Problem .............................................................................................122 Chapters: 4. Historical Information .................................................................................................... 124 5. Results and Discussion ...................................................................................................131
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