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The Synthesis and Chemistry of Strained Bicyclic Systems

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The Synthesis and Chemistry of Strained Bicyclic Systems AN ABSTRACT OF THE THESIS OF LOUIS SCERBO for the Ph. D. (Name) (Degree) in CHEMISTRY presented on S.41_0C 6 1 (Date) (Major) Title: THE SYNTHESIS AND CHEMISTRY OF STRAINED BICYCLIC SYSTEMS Abstract approved Dr. F. Thomas Bond A facile route to bicyclo(2. 1. 1)hexanes was developed involving the intramolecular photocyclization of 1, 5- hexadien -3 -one to bicyclo(2. 1. 1)hexan- 2 -one. A study of the chemistry of bicyclo- (2. 1. 1)hexan -2 -one was undertaken. Deuterium exchange and boro- hydride reduction demonstrated the strain present in the ketone. Further evidence was obtained from the failure to introduce substi- tuents alpha to the carbonyl group, a usually facile reaction and a necessary step in desired ring contraction studies. After numerous unsuccessful attempts to introduce a double bond into the bicyclo(2. 1. 1) hexane system, a successful route to the parent bicyclo(2. 1. 1) hexene was achieved. The key step involved dehydrohalogenation of 2- bromobicyclo(2. 1. 1)hexane. Some prelimi- nary studies of the olefin have been carried out and its thermolysis studied. The Synthesis and Chemistry of Strained Bicyclic Systems by Louis Scerbo A THESIS submitted to Oregon State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy June 1968 APPROVED: Assistant Professor of Chemistry in charge of major Chairman of the Department of Chemistry Dean of Graduate School Date thesis is presented VA, (\rah .ClI le g Typed by Marion F. Palmateer for Louis Scerbo ACKNOWLEDGEMENT The author wishes to express appreciation to Dr. F. Thomas Bond for assistance throughout this study and for his aid in the preparation of this manuscript. TABLE OF CONTENTS Page INTRODUCTION 1 Bicyclo( 2. 1. 1)hexanes 6 Synthesis 6 Chemistry 18 Physical Properties 23 Bicyclo(2. 1. 1)hex- 2 -yl Compounds 32 Bicyclo( 2. 1. 1)hexenes 36 Introduction 36 Synthesis 41 General Routes to Olefins 47 Bicyclo(1. 1. 1)pentanes 51 Tricyclo(2. 2. 0. 02, 6)hexanes 55 Photocycloadditions 57 Enone Photochemistry 68 RESULTS AND DISCUSSION 79 Synthesis of Bicyclo(2. 1. 1)hexan-2-one 79 1, 5- Hexadien- 3-one 79 Bicyclo(2. 1. 1)hexan- 2 -one 81 Nature of the Photochemical Cyclization 85 Utility of Bicyclo(2. 1. 1)hexan-2-one 9 5 Chemistry of Bicyclo(2. 1. 1)hexan-2-one 99 Reations at C-2 99 Reactions at C-3 103 Attempted Synthesis of Tricyclo(2. 2. 0. 02, 6)hexane 111 Bicyclo(2. 1. 1)hexenes 113 Carbene Reactions 113 Alcohol Dehydration 119 Amine Derivative Reactions 122 Dehydrohalogention 129 Page EXPERIMENTAL 140 1, 5- Hexadien -3 -ol 171 140 1, 5- Hexadien- 3 -one 149. 141 Bicyclo(2. 1. 1)hexan-2-one 66 143 Monitored Irradiations of 1, 5- Hexadien -3 -one 145 Irradiation of 1, 5- Hexadien -3 -ol 146 Sensitized Irradiation of 1, 5- Hexadien -3 -ol 146 Bicyclo(2. 1. 1)hexan -2 -ol 173 147 Bicyclo(2. 1. 1)hexan- 2 -one p- Toluene sulfonylhydra- zone 194 148 2- Oximobicyclo(2. 1. 1)hexane 193 149 2- Aminobicyclo(2. 1. 1)hexane Z09 150 N, N- Dimethyl- 2- aminobicyclo(2. 1. 1)hexane 210 151 N, N- Dimethylbicyclo(2. 1. 1)hex- 2- ylamine Oxide 211 152 N, N, N- Trimethylbicyclo(2. 1. 1)hex- 2- ylammonium Hydroxide 212 153 N, N, N- Trimethylbicyclo(2. 1. 1)hex- 2- ylammonium Iodide 213 153 N, N- Dimethylcyclohexylamine 219 154 Cyclohexene from Trimethylcyclohexylammonium Iodide 155 Pyrolysis of Trimethylcyclohexylammonium Hydroxide 156 N, N- Dimethylcyclohexylamine Oxide 220 157 Pyrolysis of N, N- Dimethylcyclohexylamine Oxide 157 Pyrolysis of N, N, -Dimethylbicyclo(2. 1. 1)hex -2- ylamine Oxide 158 Pyrolysis of Trimethylbicyclo(2. 1. 1)hex- 2- ylammonium Hydroxide 159 Reaction of Trimethylbicyclo(2. 1. 1)hex- 2- ylammonium Iodide with Butyllithium 160 3- Oximocamphor 197 161 3- Diazocamphor 198 162 3- Oximobicyclo(2. 1. 1)hexan -2 -one 199 163 Attempted Selenium Dioxide Oxidation of Bicyclo- (2. 1. 1)hexan-2-one 164 3- Hydroxymethylenebicyclo( 2. 1. 1)hexan- 2 -one 200 165 Attempted Enol Acetylation of Bicyclo(2. 1. 1)- hexan -2 -one 167 3- Bromonorcamphor 222 167 Attempted Chlorination of Bicyclo(2. 1. 1)hexan- 2 -one 168 Attempted Bromination of Bicyclo(2. 1. 1)hexan-2-one 169 3, 3, - Dideuterionorcamphor 221 169 3, 3- Dideuteriobicyclo(2. 1. 1)hexan-2-one 172 170 Page High Temperature Deuterium Exchange on Bicyclo- (2. 1. 1)hexan-2-one 171 2- Methylbicyclo(2. 1. 1)hexan-2-ol 191 172 2- Phenylbicyclo(2. 1. 1)hexan -2 -ol 192 173 Attempted Dehydration of 2- Methylbicyclo(2. 1. 1)- hexan -2 -ol 174 Reaction of 2- Phenylbicyclo(2. 1. 1)hexan-2-ol with Phosphorus Oxychloride 175 Reaction of 2- Phenylbicyclo(2. 1. 1)hexan-2-ol with a- Toluene sulfonic Acid 176 Thermal Decomposition of the Sodium Salt of Bicyclo(2. 1. 1)hexan-2-one To sylhydrazone 178 Kinetics of Base - Catalyzed Deuterium Exchange Reactions of Bicyclo(2. 1. 1)hexan -2 -one 180 Kinetics of the Sodium Borohydride Reduction of Bicyclo(2. 1. 1)hexan- 2 -one 181 2- Bromobicyclo(2. 1. 1)hexane 216 183 Bicyclo(2. 1. 1)hex -2 -ene 108 184 BIBLIOGRAPHY 186 LIST OF TABLES Table Page 1 Strain energies (S. E.) of selected compounds. 4 2 N. m. r. spectra of bicyclo(2. 1. 1)hexane derivatives. 27 3 Carbonyl stretching frequencies of selected bicyclo- (2. 1. 1)hexanones. 30 4 Rates of sodium borohydride reductions of bicyclic ketones at 25 °. 102 5 Thermal stability of 107. 115 6 Elimination reactions of bicyclo(2. 1. 1)heptylamine derivatives. 125 7 Selected infrared absorptions of strained olefins. 134 8 Vinyl proton n. m. r. chemical shifts of strained olefins (73). 135 9 Olefinic 13C -H coupling constants of strained olefins (73). 136 LIST OF FIGURES Figure Page 1 Synthetic route to 2- acetoxybicyclo(2. 1. 1)hexane- 5- carboxylic acid. 14 2 Jablonski diagram. 59 3 Electronic transitions. 60 4 Energy -level diagram for a, 3- unsaturated carbonyl compounds (45). 69 5 The n.m. r. spectrum of bicyclo(2. 1, 1)hexan- 2 -one. 8 3 6 The n. m. r. spectrum of 3, 3- dideuteriobicyclo - (2. 1. 1)hexan- 2 -one 172. 8 3 7 Photochemical cyclization reactions. 86 8 Monitored irradiation of 1, 5- hexadien -3 -one. 89 9 Synthetic routes to bicyclo(2. 1. 1)hexene. 9 5 10 Synthetic routes to bicyclo(1. 1. 1)pentane- 2- carboxylic acid. 98 11 Rates of sodium borohydride reduction of bicyclic ketone. 101 12 Rates of deuterium exchange for bicyclic ketones. 106 13 The n.m. r. spectrum of bicyclo(2. 1. 1)hex-2-ene. 133 THE SYNTHESIS AND CHEMISTRY OF STRAINED BICYCLIC SYSTEMS INTRODUCTION Many contributions to the field of organic chemistry have been derived from the study of rigid bicyclic ring systems, Such study, for the most part, has been concentrated on the bicyclo(2. 2. 1)heptane nucleus 1. The rigid geometry of this system, a 1, 4- bridged boat cyclohexane ring, results in many novel and informative chemical properties (6, 9). Much of the chemistry of 1 can be related to the 1 2 strain possessed by the system. The effects of strain on the chem- istry of 1 can be seen when this system is compared to the relatively strain-free bicyclo(2. 2. 2) octane system 2. Surprisingly, in view of the vast amount of detailed work done on the bicyclo(2. 2. 1)heptanes, very little progress has been made with the bicyclo(2. 1. 1)hexanes 3. The synthesis and chemistry of this bridged cyclopentane (or cyclo- butane) is the main subject of this thesis. 2 6 3 The revival of interest in bicyclo(2. 1. 1) hexanes during the past decade (66, 76) is based, in part, by questions which have been brought up in the study of the bicyclo(2. 2. 1)heptanes. One of the biggest problems in dealing with the chemistry of attack at C -2 of bicyclo(2, 2. 1)heptane is that such reactions can occur via exo or endo pathways. The latter of these processes is sterically unfavorable. In comparison, C -2 in 3, lies in a plane of symmetry. Attack from either side of the two- carbon bridge is an equivalent process. Thus the idea of exo or endo attack does not apply to attack at C-2 (or C-3) in bicyclo(2. 1. 1)hexanes. As a direct consequence of the symmetry in 3, however, sub- stitution at the C -5 (or C -6) position can be either exo or endo, thus allowing the study of the effect of conformation in rigid cyclobutyl ring systems. This is particularly important where participation of adjacent bonds may lead to several types of rearrangements. One may envisage the following possibilities: 3 cl> H endo C-0 H 2- substituted A second important feature of 3 is the increase in internal strain compared to 1. The geometries of these systems, which are represented below, give a qualitative indication of the differences in strain (26, 66). 4 a=95° a = 85° = p = 104° k13 = 100° é A more quantitative evaluation of the strain energies of bicyclic com- pounds has not been carried out. However, simple small -ring com- pounds and their related fused -ring systems have been studied. Some of the results for such simple systems are shown in Table 1 (8). Table 1. Strain energies (S. E. ) of selected compounds, Compound S. E. (kcal /mole)exp. S. E. (kcal /mole)calc.
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