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University Microfilms International300 N 8009261 CHANG, SOU-JEN UNY PART I: THERMAL AND PHOTOLYTIC BEHAVIOR OE DIAZOACENAPI1THENONE SYSTEMS; CHEMISTRY OF ACHNAPHTHENEQUINONE BIS (PARA-TOSYLHYDRAZONE), PART II: 5-BROMO-4-QUINOLYLDIAZOMETHANE AND 4-QUINOLYLDIAZOMETHANE: SYNTHESIS, THERMOLYSIS AND PHOTOCHEMISTRY Hie Ohio State University PH.D. 1979 University Microfilms International300 N. Zccb Road, Ann Arbor, M I 48106 18 Bedford Row, London 3VC1R 4FJ, England PART Is THERMAL AND PHOTOLYTIC BEHAVIOR OF DIAZO- ACENAPHTHENONE SYSTEMS; CHEMISTRY OF ACENAPH- THENEQUINONE BIS(o-TOSYLHYDRAZONE) PART II: 5-BROMO-^-QUINOLYLDIAZOMETHANE AND ^-QUINOLYL- DIAZOMETHANE: SYNTHESIS, THERMOLYSIS AND PHOTOCHEMISTRY. DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Sou-Jen Chang, B. Sc. The Ohio State University 1979 Reading Committee: Approved By Professor Mathew A. Plats Professor Harold Shechter Professor John S. Swenton Advisor Department of Chemistry DEDICATION for Mr. and Mrs. Y.-T. Chang, my parents, without whom this would not have been possible ACKNOWLEDGMENTS I wish to express my sincere gratitude to Professor Harold Shechter for his intellectual quidance arid inspiration during the course of this research. His patience, encouragement and understanding should not be forgotten. I would also like to extend my appreciation to the Ohio State University, the National Science Foundation and the National Institutes of Health for their financial support. VITA November 10, 1950...........Born-Taiwan, Republic of China. 1973......................... B. Sc. National Taiwan Normal University. 1973-1975.................... Teaching Assistant, Department of Chemistry, National Taiwan Normal University; Research Chemist, Department of Chemistry, Academia Sinica, Taipei, Taiwan. 1975-1977................... Teaching Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio. 1977-1979................... Research Associate, Department of Chemistry, The Ohio State University, Columbus, Ohio. TABLE OF CONTENTS Page DEDICATION............................................ ii ACKNOWLEDGMENTS....................................... iii VITA................................................... iv LIST OF TABLES AND FIGURES........................... vii PART Is THERMAL AND PHOTOLYTIC BEHAVIOR OF DIAZO- ACENAPHTHENONE SYSTEMS j CHEMISTRY OF ACENAPHTHENEQUINONE BIS(jd-TOSYLHYDRAZONE) . 1 STATEMENT OF PROBLEM........................ 2 HISTORICAL................................... 6 RESULTS AND DISCUSSION...................... 38 SUMMARY...................................... 96 EXPERIMENTAL................................ 98 PART II: 5-BR0M0-4-QUIN0LYLDIAZ0METHANE AND '+-QUINOLYLDIAZOMETHANE s SYNTHESIS, THERMOLYSIS AND PHOTOCHEMISTRY............. 1^3 STATEMENT OF PROBLEM........................ 1^1 HISTORICAL................................... 14? RESULTS AND DISCUSSION...................... 157 SUMMARY...................................... 176 v CONTENTS (CONT’D) Page EXPERIMENTAL................................ 1?8 REFERENCES PART 1........................................... 198 PART II.......................................... 203 vi LIST OF TABLES Table Page 1 Bond Angles(°) and Bond Distances(A0) of ^2 and ............................................... 153 LIST OF FIGURES Figure 1 Diagram of 1-Bromo-lH-cyclobutafde]naphthalene (2).................................................. 1^5 vii PART I THERMAL AND PHOTOLYTIC BEHAVIOR OF DIAZOACENAPHTHENONE SYSTEMS; CHEMISTRY OF ACENAPHTHENEQUINONE BIS(£-TOSYLHYDRAZONE) 1 STATEMENT OF PROBLEM Recently lH-cyclobuta [de]naphthalene (1), 1-methylene- lH-cyclobuta [de] naphthalene (2 ) and its derivatives, and lH-cyclobuta [dejnaphthalen-l-one (^) have been prepared in this laboratory'1'. These unusual molecules have been found 2 (1) (a) R. J. Bailey, Ph. D. Dissertation, The Ohio State University, 197^; (b) P. Card, Ph.D. Dissertation, The Ohio State University, 1976; (c) F. Friedli, Ph.D. Dissertation, The Ohio State University, 1978* to be surprisingly stable1" and their chemistry1" is of great interest at present. As yet however the preparative methods for 1-^, their derivatives, and their analogs are lengthy, inversatile, and unadaptable for large-scale synthesis. A study has been presently made of the chemistry of various 2 3 diazoacenaphthenone derivatives ((+). The principal objectives of this effort are (1 ) to determine the electronic and steric effects of substituents in inducing possible Wolff rearrangements of k to their corresponding ketenes, 1H- cyclobutafde]naphthalen-l-ylidenemethanone derivatives (6 ), as in equation 1 , (2 ) to study the various insertion and -> Z Z 7 Z capture reactions of the intermediate alpha-ketocarbenes £ derivable from thermolysis, photolysis, and metal ion- catalyzed decompositions of 4, and (3 ) to elaborate various 1 ,3-dipolar addition reactions of 4 with appropriate acceptor substrates. The specific diazo ketones selected for this research are: diazoacenaphthenone (£), 2-diazo-5-nitroace- naphthenone (8 ), 2-diazo-5 ,6-dinitroacenaphthenone (§), 2 -diazo-3 »S-dimethoxyacenaphthenone (10) and 2-diazoace- anthrenone (11). OCH 10 11 A further aspect of this research is investigation of base-catalyzed decomposition of acenaphthenequinone bis(jc- tosylhydrazone) (12). One of the objectives is to study possible generation of 1 ,2-bisdiazoacenaphthene (1^) and its subsequent decomposition to acenaphthylyne (1^-) as in equation 2. Acenaphthylyne (1^) is of our interest because TosHNN NNHTos 2B -2N, -> -> (2) -2B ,-Toj 12 of its structural similarity to benzyne and it is expected to have significant reactivity in cycloaddition and with various electrophiles and nucleophiles. In this work, some interesting results have been observed and will be presented. HISTORICAL 1-Bromo-lH-cyclobuta [de]naphthalene (12)» the first naphthalene bridged in its 1,8 positions by a single carbon 2 atom moiety, has been synthesized by photolysis of either 8-bromo-l-naphthaldehyde p-tosylhydrazonate (1£) or 8-bromo- 1-naphthyldiazomethane (16) in ether (Eq 3)» Bromide 12 ®Na H=NNTos © 15 (3) B CHN, 11 16 is surprisingly stable and is storable for long periods in air at room temperature. X-Ray^ analysis reveals that 12 is planar and that much of the strain in its cyclobutane section is relieved by accommodation within its naphthalene moiety. 7 (2) R. J. Bailey and H. Shechter, J. Amer. Chem. Soc., 96, 8116 (197*0 - . (3) M. A. Gessner, Master's Thesis, The Ohio State University, 1977. Bromide 1£ undergoes a series of nucleophilic displacements to give stable bridged compounds. For example, treatment of 1£ with sodium azide yields 1 -azido- lH-cyclobuta [de] naphthalene (18, 9^ » Eq *0 • Similar NaN^ (*0 HMPA 18 displacements have been effected with lithium aluminum hydride, sodium thiophenoxide, potassium cyanide, etc. The Grignard reagent (lg) of 1£ is easily prepared and is usuable as a typical organometallic synthon. Thus, acidification of lg yields lH-cyclobuta [de] naphthalene (20, Eq 5)i displacement of methyl iodide gives 1-methyl-lH- cyclobuta Qi§3 naphthalene (21), and carboxylation and hydrolysis results in lH-cyclobuta OieJ naphthalene-1- carboxylic acid (22, Eq 5). 8 20 H MgBr CH 11 + Mg (5) 12 21 1) co^ 2) H^O® 22 The varied chemistry of 1£ and lg is summarized further in the Ph.D. dissertations of Baileyla, Cardlb, and Friedlilc, lH-cyclobuta[d§] naphthalene (20) is also a stable, readily handled, planar hydrocarbon. Its structure is very 3 similar to that of VJ< Electrophilic substitution of 20 by various reagents occurs efficiently at the C-^ and C-5 9 positions and without destruction of the four-membered ring. Thus, nitration of 20 with nitric acid in sulfuric acid or acetic acid produces 4-nitro-lH-cyclobuta [de] naphthalene (2^) and 4,5-dinitro-lH-cyclobuta[le]naphthalene (24, Eq 6 ). HNO (6) NO NO 2 2 20 24- Similar substitutions have been effected with acetyl chloride/ aluminum chloride and bromine and iron. The cyclobutyl ring of 20 is cleaved by hydrogenation however to give 1-methylnaphthalene (2£, Eq 7). H. H H, (7) 10% Pd-C 20 25 Of significance to the purposes of the present proposal for synthesis of ketenes such as 6 is that bromide 1£ reacts with triphenylphosphine to form phosphonium bromide 26 which is converted efficiently by sodium dimsylate to phosphorane 10 22 (Eq 8). The strained Wittig reagent 2£ reacts rapidly H ®PPh3 Br0 PPh © © CHoS0CH0 Na 11 CH-SOCH -NaBr 26 11 (8 ) 28, R^R^CH- -Ph^PO j ^ „1 „ „2 22, R = Ph, R = H. with a wide variety of aldehydes and ketones to give the highly strained products, 1-alkylidene-lH-cyclobuta[de] - naphthalenes in high yields (Eq 8 ). Thus acetone and benzaldehyde condense with 2£ to form 1-isopropylidene- lH-cyclobuta[de] naphthalene (28) and 1-benzylidene-lH- cyclobuta[de] naphthalene (2g), respectively. Olefins such as 28 and 22 are quite stable and undergo a wide variety of electropholic and free-radical addition reactions'^’ with retention of the cyclobutanoid moiety. Reduction of 28 with hydrogen over palladium on carbon does result in cleavage of the four-membered ring to give 11 1-isobutylnaphthalene (^2 * ^q 9 )• CH CH Pd/C 28 30 ^ m Ni rv At elevated temperature, 1-methylene-lH-cyclobuta- [de]naphthalene (2 ) undergoes cleavage of its cyclobutyl ring and subsequent hydrogen migration to give 1-naphthyl- acetylene (^1* 73$>» Eq 10). The temperatures necessary 550 (10) 0.1 mm 2 21 for this isomerization is indicative of the thermal stability
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