Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1978 Part I: An investigation of the rehybridization of bridgehead olefins, solvolytic formation of bridgehead olefins. aP rt II: The effect of silver(I) ion upon the solvolysis products in the dibromo-and monobromobicyclo[6.1.0]nonane systems Richard Francis Palmer Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Palmer, Richard Francis, "Part I: An investigation of the rehybridization of bridgehead olefins, solvolytic formation of bridgehead olefins. Part II: The effect of silver(I) ion upon the solvolysis products in the dibromo-and monobromobicyclo[6.1.0]nonane systems" (1978). 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The majority of users indicate that the textual content is of greatest value, however, a somewhat higher quality reproduction could be made from "photographs" if essential to the understanding of the dissertation. Silver prints of "photographs" may be ordered at additional charge by writing the Order Department, giving the catalog number, title, author and specific pages you wish reproduced. 5. PLEASE NOTE: Some pages may have indistinct print. Filmed as received. University Microfilms International 300 North Zeeb Road Ann Arbor, Michigan 48106 USA St. John's Road, Tyler's Green High Wycombe, Bucks, England HP10 8HR 78132*0 PALMER, RICHARD FRANCIS PART lî AN INVESTIGATION OF T'":E REHYBRIDIZATICN GF BRIDGEHEAD OLEFINS, SOLVOLYTIC FORMATION Qf SRIDGE^EAD OLEFINS. PA^T II: THE EFFECT OF SILVEHCI) ION UPON THE SOIVOLYSIS PRODUCTS TKE DlgRO^O- AND M0NO9R0MOgICYCLD(b.l.C)HONANE SYSTEMS. lO^A STATE UNIVERSITY, PH.n,, 1976 Universiç/ Micnônims International 300 nze.eb road, amn arbor, mi «sioe Part I: An investigation of the rehybridization of bridgehead olefins, solvolytic formation of bridgehead olefins. Part II: The effect of silver(I) ion upon the solvolysis products in the dibromo- and monobromobicyclo[6.1.O]nonane systems. by Richard Francis Palmer A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OP PHILOSOPHY Department: Chemistry Major: Organic Chemistry Approved: Signature was redacted for privacy. :n Cha^e of Major Work Signature was redacted for privacy. F 01 Tient Signature was redacted for privacy. For College Iowa State University Ames, Iowa 1978 11 TABLE OP CONTENTS Page PART I: AN INVESTIGATION OF THE REHYBRIDIZATION OF BRIDGEHEAD OLEFINS, SOLVOLYTIC FORMATION OF BRIDGEHEAD OLEFINS 1 INTRODUCTION 2 RESULTS AND DISCUSSION 47 EXPERIMENTAL 122 PART II: THE EFFECT OF SILVER(I) ION UPON THE SOLVOLYSIS PRODUCTS IN THE DIBROMO- AND MON0BR0M0BICYCLO[6.1.0]NONANE SYSTEMS l8l INTRODUCTION 182 RESULTS AND DISCUSSION 194 EXPERIMENTAL 214 • BIBLIOGRAPHY 227 ACKNOWLEDGMENTS 24l iii LIST OF FIGURES Twisting distortion 18 Planar deformation 18 Nonplanar deformation 18 Potential energy curves as a function of the angle of rotation about the double bond in ethylene (64d) 19 Distortion of ir-bond in ^ 24 Distortion of w-bond in ^ 24 Distortion of u-bond in 22 24 Distortion of ir-bond in 71 24 Unrehybridized bridgehead olefin 46 Rehybridized bridgehead olefin 46 NMR (top, 60 Mcps) and infrared (bottom) spectra of anti-ll-bromo- ll-chlorotricyclo[4.4.1.0^'^]undec- 3-ene (89c) 49 NMR (top, 60 Mcps) and infrared (bottom) spectra of syn-ll-bromo- ll-chlorotricyclo[4.4.1.0^'^]undec- 3-ene (89b) 50 NMR (top, 60 Mcps) and infrared (bottom) spectra of 11-bromo-ll-chloro- tricyclo[4.4.1.0^'^]undecane (87b) 51 NMR spectrum (60 Mcps) of 11,11- dibromotricyclo[4.4.1.0^'^]undec-3-ene (89a) 52 NMR spectrum (60 Mcps) of 11,11- 1 -6 dichlorotricyclo[4.4.1.0 ' ]undec-3-ene Iv l6. H NMR (top, 100 Mcps) and Infrared (bottom) spectra of 11-chloro-l,6- dihydroxyblcyclo[4.4.l]undecane (TZ5a) 58 17- NMR (top, 100 Mcps) and infrared (bottom) spectra of anti-ll-chloro-6- hydroxybicyclo[4.4.l]undec-l(2)-ene (145) 59 18. NMR (top, 60 Mcps) and infrared (bottom) spectra of 1-bromochloro- methylbicyclo[4.4.0]dec-5-ene (146) 63 19. NMR (top, 60 Mcps) and infrared (bottom) spectra of 11-chloro-l,6- diacetoxybicyclo[4.4.l]undecane (149) 64 20. NMR (60 Mcps) spectrum of 11-chloro- tricyclo[4.4.1.0^'^]undec-2-ene (147) 65 21. NMR (top, 60 Mcps) and infrared (bottom) spectra of bicyclo[4.4.0]dec- 5-ene-l-carboxaldehyde (151) 69 22. NMR (top, 60 Mcps) and infrared (bottom) spectra of 7-acetoxybicyclo- [5.4.0]undecan-2-one (153) 70 23- NMR (top, 100 Mcps) and infrared (bottom) spectra of anti-ll-chloro-1,6- dihydroxybicyclo[4.4.1Jundec-3-ene (T77) 90 24. NMR (top, 100 Mcps) and infrared (bottom) spectra of cis-7-hydroxybicyclo- [5.4.0]undec-4-en-2-one (180) 91 25. NMR (top, 100 Mcps) and infrared (bottom) spectra of syn-ll-chloro-1,6- dihydroxybicyclo[4.4.1Jundec-3-ene C176) 92 26. NMR (top, 100 Mcps).and infrared (bottom) spectra of anti-ll-chloro- bicyclo[4.4.I]undec-l,3-dien-6-oI (T69a) 95 27. NMR (top, 100 Mcps) and infrared (bottom) spectra of (IIR, 6S) and (lis, 6Rj-ll-chloroblcyclo[?\4.1]undec- l(10),3-dien-6-ol (ITOb) 96 V Figure 28, H NMR (top, 100 Mcps) and infrared (bottom) spectra of 6-chloroinethylene- cyclodec-3-enone (171 and 172) 98 Figure 29, NMR (top, 100 Mcps) and infrared (bottom) spectra of a mixture of cis- 7-hydroxybicyclo[5.4.0]undec-9-en-2-one (173) and anti-ll-chloro-1,6-dihydroxy- bicyclo[4.4.lJundec-3-ene (177) 99 Figure 30, NMR (60 Mcps) spectrum of bicyclo- [5.4.0]undec-l(7),9-dien-2-one (9^) 100 Figure 31a. NMR (top, 60 Mcps and bottom, 100 Mcps) spectra of cis-tricyclo- [5.4.0.0^''^]undec-3-en-2-one (175) 101 Figure 31b. Infrared spectrum of cis-tricyclo- [5.4.0.05'f]undec-3-en-2-one (175) 103 Figure 32. NMR (top, 60 Mcps) and infrared (bottom) spectra of cis-bicyclo- [4.4.0]dec-3-ene-l-carboxylic acid (178) 106 Figure 33. NMR (top, 100 Mcps) and infrared (bottom) spectra of trans-bicyclo- [4.4.0]dec-3-ene-l-carboxylic acid (179) 107 Figure 34. NMR (top, 100 Mcps) and infrared (bottom) spectra of tran s-6-hydr oxy- bicyclo[4.4.0]dec-3-ene-l-carboxylic acid (174) 108 Figure 35. NMR (top, 100 Mcps) and infrared (bottom) spectra of 6-chloromethylene- cyclodec-3-enone (171) 113 Figure 36. NMR spectrum (100 Mcps) of trans- l-bromo-9-hydroxycyclononene (212a) 196 Figure 37. NMR spectrum (100 Mcps) of cis-1- bromo-9-hydroxycyclononene (2T6a) I96 Figure 38. Plot of data in Table 14 200 Figure 39. Plot of data in Table 15 201 vi Figure 40. NMR spectrum (100 Mcps) of cis-3- hydroxycyclononene (208a) 202 Figure 41. NMR spectrum (100 Mcps) of trans- 3-hydroxycyclononene (207a) 202 Figure 42. Plot of data in Table l6 205 vli LIST OF TABLES Page Relative acetolysis constants of en'do and exo-bicyclo[n.1.0]alkyl-p- toluenesulfonates 29 NMR data for compounds ^ and '89^ 53 Mass spectral results 56 Areas from NMR 56 Per cent deuterium in ^ of T4'la and =7,10 56 Mass spectral intensities for enones at 70 ev 78 NMR data for monocyclic ketones 124 a-c 83 Mass spectral intensities for 11-bromo- ll-chlorotricyclo[4.4.1.0^'^]undecane (average of five runs) 134 Intensities (I) of ions containing other than 2 deuterium atoms I[deuterated m/e(M)]-I[undeuterated m/e(M-2)] 135 Ratio of areas (from Table 4) of NMR data 137 Weights (in grams) of 89e and 89f obtained from methanolysis with 20 fold excess silver perchlorate 176 Weights (in grams) of 89e and 89f obtained from methanolysis with stoichiometric amount of silver perchlorate 178 Weights (in grams) of 89e and 89f obtained from hydrolysis with 5 fold excess of silver perchlorate 179 vlli Table 14.