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University Microfilms, Inc., Ann Arbor, Michigan the SYNTHESIS of UNSATURATED HETEROCYCLIC This dissertation has been 69-15 948 microiihned exactly as received PHILIPS, Judson Christopher, 1942» THE SYNTHESIS OF UNSA.TURATED HETEROCYCLIC AND CARBOCYCLIC PROPELLANES. The Ohio State University, Ph.D,, 1969 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan THE SYNTHESIS OF UNSATURATED HETEROCYCLIC AND CARBOCYCLIC PROPELLANES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Judson Christopher Philips, B.S. The Ohio State University 1969 Approved by AdviserL s e r l ) - Department of Chemistry DEDICATION To my parents XI ACKNOWLEDGMENTS The author is indebted to Professor Leo A. Paquette for his constant guidance and encour­ agement . The author acknowledges the financial support from a National Institutes of Health Predoctoral Fellowship. The author thanks Mr. Tedd E. Dawson, Mr. Lawrence A. Levine (National Science Foundation Undergraduate Research Participant, summer 1967)3 and Mr. Robert Sanitra for technical assistance in the preparation of starting materials. 1x 1 VITA November 15, 19^2 ...... Born - Glen Ridge, New Jersey 1964 ................... B.S., The Pennsylvania State University, University Park, Pennsylvania 196^-1965 .............. Teaching Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio 1965-I966 .............. Research Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio 1966-I968 .............. National Institutes of Health Predoctoral Fellow PUBLICATIONS Herman G. Richey, Jr., J. Christopher Philips, and Leonard E. Rennick, "Alkynyl Cations," J. Amer. Chem. Soc., 8%, I38I (1965). Herman G. Richey, Jr., Leonard E. Rennick, Arthur S. Kushner, Jane M. Richey, and J. Christopher Philips, "The Tripropynylcarbonium Ion," J. Amer. Chem. Soc., 8T, ^017 (I965). Leo A. Paquette and J. Christopher Philips, "New Convenient Syntheses of Substituted Cyclobutenes," Tetrahedron Letters, U6U5 (1967). Leo A. Paquette and J. Christopher Philips, "Concerning Azacycloocta- tetraene Valence Tautomerism. Preparation of Annelated 7-Azabicyclo- [4.2.0]octa-2,4,7-trienes," J. Amer. Chem. Soc., 90, 3898 (1968). FIELDS OF STUDY Major Field: Organic Chemistry IV TABLE OF CONTENTS Page DEDICATION.............................................. il ACKNOWLEDGMENTS ......................................... ill VITA..................................................... iv LIST OF FIGURES ......................................... vi LIST OF ILLUSTRATIONS ................................... vii LIST OF TABLES........................................... viii INTRODUCTION ............................................ 1 RESULTS AND DISCUSSION PART I. Azocines and Unsaturated Azapropellanes .... 20 PART II. Unsaturated Carbocyclic Propellanes ....... 44 EXPERIMENTAL............................................ 69 BIBLIOGRAPHY ............................................ 113 LIST OF FIGURES Page FIGURE 1. The partial 60 MHz nmr spectra of some azocines and azocine valence isomers........................ 2k FIGURE 2. The partial 60 MHz nmr spectra of l$-ethoxy-12-aza- [$.4.2]propella-8,10,12-triene (ll6a ).............. $6 FIGURE 5- The partial 100 MHz nmr spectrum of [U.U.2]propella- 2,^^11 -triene (1 2 8)................................ 51 FIGURE U. The 100 MHz nmr spectrum of [4.^.2]propella- 2,^^7,9,11 -pentaene ( ^ ) ........................... 64 VI LIST OF ILLUSTRATIONS Page SCHEME I. Synthetic Approach to ll-Ethoxy-10-aza[^.5.2]- propella-2,^,10-triene (76a) and 12-Ethoxy-ll- aza[if.^.2]propella-2,U,ll-triene (76b ) ......... 21 SCHEME II. Synthetic Approach to 2-Methoxy-l-azocine (lOOa) and 3,T-Dimethyl-2-methoxy-l-azocine (100b) .... 28 SCHEME III. Synthetic Approach to l$-Ethoxy-12-aza[5.^.2]- propella-8jl0 ,12-triene (ll6a ) and lU-Ethoxy-15- azabi cy d o [6.k .2]tetrade ca-8,1 0 ,1 2,1 $-tetraene (118 ) 33 SCHEME IV. Synthetic Approach to 12-Ethoxy-ll-aza[4.^.2]- propella-2,k^7,9,ll-pentaene (II9) ............. ^ SCHEME V. Synthetic Approach to [4.4.2]Propella-2,^,ll- triene (1 2 8) ................................... 48 SCHEME VI. Ramberg-Backlund Approach to [4.4.2]Propella- 3.8.11 -triene (l4$) ............................ 56 SCHEME VII. Alternate Synthetic Approach to [4.4.2]Propella- 3.8.11 -triene (l43) ............................ 60 SCHEME VIII. Synthetic Approach to [4.4.2]Propella-2,4,7,9,ll- pentaene (67) .................................... 62 V I 1 LIST OF TABLES Page TABLE 1. Chemical Shift Data for Some 1,3-Cyclohexadienes ... 65 TABLE 2. Ultraviolet Data for Some 1,3-Cyclohexadienes 66 TABLE 3- Mass Spectral Data of Some Unsaturated Heterocyclic and Carbocyclic Propellanes ............. 112 Vlll INTRODUCTION The synthesis, structure and reactivity of unsaturated cyclic molecules represent an area of investigation which has fascinated organic chemists for over a century. The high degree of unsaturation in benzene (l) and its failure to undergo addition reactions proved difficult for chemists to rationalize. While Kekule’s deduction of 1 an oscillating structure for benzene satisfactorily explained the known chemistry of this hydrocarbon, it provided no rationale for the remarkable difference in the reactivity of benzene and ordinary ole­ fins. This fluctuating cyclohexatriene theory is no longer tenable. The 6jt electrons of benzene are evenly delocalized over the six carbon atoms resulting in a completely symmetrical a and jt framework. 2 The multistep synthesis of cyclooctatetraene (2) by Willstatter, and the discovery that this polyene possesses normal olefinic proper­ ties only served to emphasize further the unusual aromatic character of benzene. With the development of Huckel molecular orbital theory in the 3 1950’s, chemists began to gain an understanding of the relationship ■between aromatic character and molecular structure. The scope and ramifications of the aromaticity concept have been the subject of 4-7 a number of reviews. Although the Huckel method has been criti­ cized in recent years, the Huckel (Un + 2) rule has served well as a predictive tool in the development of aromatic theory. In essence, this rule states that ’ 'those monocyclic coplanar systems of trigonally hybridized atoms which contain (Un + 2)% electrons will possess relative 9 electronic stability.'' Some examples of systems adhering to this rule are depicted below. Me Me 10 In polycyclic cases, such as trans-l^,l6-dimethyldihydropyrene (6) 11 and acepleiadylene (T)j the periphery of the it system is considered 12 in the application of the rule. Unfortunately there is no satisfactory, concise definition of 4 aromaticity. Chemists rely on a number of physical and chemical properties as criteria for aromatic character; a) Possession of a large negative resonance energy as determined from heat of combustion or hydrogenation data. b) The propensity to undergo electrophilic substitution rather than addition reactions. c) Observation of a it electron induced ring current, most readily observable by nmr spectroscopy. If ''stabilization by delocalization'' is designated as a working definition of aromaticity, what can be said of conjugated cyclic it systems which do not manifest this aromatic character, e.g, 4nn-elec- tron systems? While simple Huckel molecular orbital calculations 9 , predict a delocalization energy of zero for cyclobutadiene (square geometry 8), more sophisticated calculations predict resonance de- 6 ,13,14 stabilization for such a cyclobutadiene structure. Dewar's 15 16 calculations and the experimental results of the Pettit group o 8 10 indicate a rectangular structure (9) with alternating single and double bonds for cyclobutadiene. The cyclopropenyl anion (lO) is 6 ,13,14 a similar case. Breslow has designated these systems, which are predicted to manifest destabilization by electron delocalization, 6 ,13,14 as antiaromatic. The base-catalyzed deuterium exchange of 1,2- diphenyl-5-benzoylcyclopropene (ll) i s 6000 times slower than that 13 of the corresponding cyclopropane 12. This dramatic rate retarda- ,C— 0 0 0 HH 11 12 tion is convincing evidence in support of the antiaromaticity hy­ pothesis. Cyclodecapentaene ( [lO]annulene) is an interesting (Un + 2)n~ electron system for which a number of geometries (e.g., 13-1^) are possible. Cyclodecapentaene 13 contains two trans double bonds. 13 Ih 15 and the steric interference of the internal 1,6-hydrogen atoms can be expected to produce significant distortion from planarity. The all ci8 structure lU suffers from angle strain (bond angles of lUU°), but the recent synthesis of the presumably planar cyclononatetrenyl anion (_^) with bond angles of lUO° would seem to deemphasize the importance of this type of strain. Attempts to produce a cyclode- o 16 IT 18 capentaene via thermal or photochemical valence isomerization of cis- 18 9,10-dihydronaphthalene (IT) have been unsuccessful. Low tempera­ ture photoisomerization of trans-9,10-dihydronaphthalene (l8) gave an unstable product (perhaps the all cis cyclodecapentaene lU) which 19 could be hydrogenated to cyclodecane with diimide. Mono-trans- LlO]annulene (l^) has been postulated as an intermediate in the con­ version of bicyclo[6.2.0]deca-2,4,6,9-tetraene (19) to trans-9,10- 20 dihydronaphthalene (18), and the synthesis of a mono-trans-tribenz- 21 [lOJannulene 20 has been reported. 19 15 18 20 In an interesting series of experiments designed to alleviate the internal 1,6-hydrogen eclipsing in [lOjannulene Vogel and co-workers have synthesized a
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