Synthesis of Alkylated Benzenes and Lithium Aluminium Hydride Reduction

Total Page:16

File Type:pdf, Size:1020Kb

Synthesis of Alkylated Benzenes and Lithium Aluminium Hydride Reduction 70 - 14,004 DAUERNHEIM, Lauren William, 1938- SYNTHESIS OF ALKYLATED BENZENES AND LITHIUM ALUMINUM HYDRIDE REDUCTION OF 1,3-DIHALIDES. The Ohio State University, Ph.D. , 1969 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED SYNTHESIS OP ALKYLATED BENZENES AND LITHIUM ALUMINUM HYDRIDE REDUCTION OF 1,3-DIHALIDES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Lauren William Dauernheim, B.A., M.A ****** The Ohio State University 1969 Approved by Adviser Department of Chemistry ACKNOWLEDGMENT I am thankful for having had the opportunity to work under Dr. Melvin S. Newman. His guidance and support made fulfillment of this research possible. ii VITA February 16, 1938 , ....... Born, St. Louis, Missouri 1960 ...................... A.B., Washington University St. Louis, Missouri 1963 M.A., University of Arizona Tucson, Arizona iii TABLE OF CONTENTS Page ACKNOWLEDGMENTS ................................... ii VITA ............................................. iii LIST OF TABLES.................................... v LIST OF FIGURES ................................... vi LIST OF C H A R T S ......... vii PART I. SYNTHETIC ROUTES TO CERTAIN ALKYLATED BENZENES INTRODUCTION ................................ 1 SYNTHETIC ROUTES TO ALKYLATED NEOPENTYLBENZENES . 12 SYNTHETIC ROUTES TO ALKYLATED ETHYLBENZENES ........ 20 PART II. SYNTHESIS AND LITHIUM ALUMINUM HYDRIDE REDUCTION OF CERTAIN 1,3-DIHALOPROPANES INTRODUCTION ..................................... 23 SYNTHESIS OF 2-BENZYL-2-METHYL-1,3-DIHALOPROPANES . 25 SYNTHESIS OF 2-BENZYL-l,3-DIHALOPROPANES .......... 27 DISCUSSION OF THE NMR SPECTRA OF 2-BENZYL-l,3- DIHALOPROPANES ................................. 29 RESULTS AND CONCLUSIONS FROM THE LITHIUM ALUMINUM HYDRIDE REDUCTION OF CERTAIN 1,3-DIHALOPROPANES . 33 EXPERIMENTAL OF PART I ............... 43 EXPERIMENTAL OF PART I I ............................ 63 iv LIST OF TABLES Table Page I,. Reduction of Certain 2-Benzyl-l,3-dihalides with Lithium Aluminum Hydride .............. 79 II. Product Distribution from LAH Reduction of 2-Benzyl-2-methyl-l,3-dichloropropane .... 83 III. Product Distribution from LAH Reduction of ! 2-benzyl-2-methyl-l,3-dibromopropane .... 84 IV. Product Distribution from Competitive Reduction of 2-Benzyl-2-methyl-l,3- diiodopropane and 2-Benzyl-2-methyl-l- iodopropane................................ 86 V. Product Distribution on Reduction of 2-Benzyl- 1,3-diiodopropane .......................... 87 VI. Product Distribution on Competitive Reduction of 2-Benzyl-2-methyl-l,3-diiodopropane and 2-Benzyl-l,3-diiodopropane ................ 89 v LIST OF FIGURES Figures Page 1. Structures of Silver and Halogen IT -Complexes............................... 2 2. Partially Hindered Faces in O-Dineopentyl- tetramethylbenzene . ...................... 5 3. View of Angular Dependence on Hyperconjuga­ tion ............................. 9 4. Some Possible Rotomers in Alkyl Benzenes . 10 5. Possible Rotomers of 2-Benzyl-l,3- dihalopropanes ........................... 30 6. Partial NMR Spectrum of 2-benzyl-l,3- dibromopropane ............. 30 7. Partial NMR Spectrum of 2-benzyl-l,3- dibromopropane at 90° C ........... 31 8. Partial NMR Spectrum of 2-benzyl-l,3- dichloropropane ............................ 31 9. Partial NMR Spectrum of 2-benzyl-l,3- dichloropropane at 100° C .................. 32 10. Partial NMR Spectrum of 2-benzyl-l,3- diiodopropane .............................. 32 11. Partial NMR Spectrum of Benzylcyclopropane . 76 12. Partial NMR Spectrum of 2-Benzyl-l- iodopropane ......... .............. 77 vi LIST OF CHARTS Chart Page I. Synthesis of 1,3,5-Trimethyl-2,4- dineopentylbenzene......... , . 13 II. Synthesis of 1,2,4,5-Tetramethyl-3- neopentylbenzene .......................... 16 III. Synthesis of l,2,3,5-Tetrarnethyl-4- neopentylbenzene....................... 18 IV. Attempted Synthesis of 1,2,5-Trimethyl-3,4- dineopentylbenzene ........................ 19 V. Partial Synthesis of Ethyl-2,3,4,6- tetramethylbenzene ................ .... 21 VI. Synthesis of 2-Benzyl-2-methyl-l,3- dihalopropanes ..... ........ ..... 26 VII. Synthesis of 2-Benzyl-l,3-dihalopropanes . 28 VIII. Reaction Pathways in LAH Reduction of Certain 1,3 Dihalides .................... 33 vii LIST OF CHARTS Chart Page I. Synthesis of l,3,5-Trimethyl-2,4- dineopentylbenzene......... 13 II. Synthesis of l,2,4,5-Tetramethyl-3- neopentylbenzene .......................... 16 III. Synthesis of l,2,3,5-Tetramethyl-4- neopentylbenzene .......................... 18 IV. Attempted Synthesis of l,2,5-Trimethyl-3,4- dineopentylbenzene ........................ 19 V. Partial Synthesis of Ethyl-2,3,4,6- tetramethylbenzene ........................ 21 VI. Synthesis of 2-Benzyl-2-methyl-l,3- dihalopropanes ........................... 26 VII.Synthesis of 2-Benzyl-l,3-dihalopropanes . 28 VIII. Reaction Pathways in LAH Reduction of Certain 1,3 Dihalides .................... 33 vii PART I ^Synthetic Routes to Certain Alkylated Benzenes -I. Introduction Statement of Problem Synthetic routes to 1,3,5-trimethyl-2,4-dineopentyl- benzene and l,2,5-trimethyl-3,4-dineopentylbenzene were explored. These compounds might give information on the participation of hypothetical Tf-complexes in certain aromatic nitration and bromination reactions. The synthesis of l,2,4,5-tetramethyl-3-neopentylbenzene, l,2,3,5-tetramethyl-4-neopentylbenzene, and the partial syn­ thesis of l,2,4,5-tetramethyl-3-ethylbenzene and 1,2,3,5- tetramethyl-4-ethylbenzene was undertaken. In future studies, these compounds might yield information on the importance of steric restrictions on alkyl hyperconjugation in aromatic bromination. Discussion of TT-Complexes in Aromatic Substitution The geometries of the TT-complexes between the silver ion and benzene and the bromine molecule and benzene have been determined by X-ray methods. Infrared and Raman absorption, dipole moment, and charge transfer absorption data also relate to the geometry of halogen TT-complexes with benzene. Studies of the X-ray crystal structure of the TT-complex between silver perchlorate and benzene showed the silver ion associated with four carbon atoms but not with the six-fold axis of symmetry in benzene. ' The 1. R. E. Rundle and J. H. Goring, J. Am. Chem. Soc., 72, 5337 (1950) . 2. H. G. Smith and R. E. Rundle, J. Am. Chem. Soc., 80, 5075 (1958). silver ion is associated with two carbon atoms on a benzene ring above it and with two carbon atoms on a ring below it as shown in figure 1. In a theoretical treatment the same structure was concluded for the silver complex with benzene.^ 3. R. S. Mulliken, J. Am. Chem. Soc., 74, 881 (1952). Figure 1 Structures of Silver and Halogen Tf-Complexes X-ray studies on crystalline 1:1 adducts of benzene with bromine and chlorine show that the components of the 4 5 TT -complex have the axial model geometry (figure 1). ' An 4 . O. Hassel and K. O. Stromme, Acta Chem. Scand.r 12, 1146 (1958). 5. O. Hassel and K. 0. Stromme, Acta Chem. Scand., 13, 1781 (1959). “ analysis of infrared and Raman active bands in the benzene- bromine complex and benzene-iodine Tf-complex supports an axial model which places the bromine and iodine molecules coincident with the benzene six-fold axis.® A study of the 6. E. E. Ferguson, J. Chem. Phys., 25, 577 (1956). infrared spectrum of the hexadeuterobenzene-iodine complex leads to the same conclusion. A dipole moment study and 7. E. E. Ferguson, Spectrochim. Acta, 1£, 123 (1957). calculations corresponding to the charge-transfer absorption maximum for the benzene - iodine complex are also in agree­ ment with the axial model,® 8. K. Fukui, A, Inamura, T. Yonezawa, and C. Nagata, Bull. Chem. Soc. Japan, 35, 33 (1962). Theoretical calculations support a less symmetrical Q model for the iodine - benzene complex. This possibility 9« R. S. Mulliken, J. Chem. Phys., 23^, 397 (1955). can not be completely ruled out in solutions, although experimental evidence favors the axial model. Work in this laboratory has shown that hindrance near the six-fold axis of symmetry of the pTT orbitals of o-dineopentyltetramethylbenzene can effect the equilibrium constant of the tetracyanoethylene Tf-complex.*® The ortho, 10. M. S. Newman, J. R. Le Blanc, H. A. Karnes, and G. Axelrad, J. Am. Chem. Soc., ££, 868 (1964). meta, and para isomers of tetramethyldineopentylbenzene were prepared. Molecular models indicated that only o-dineopentyl- tetramethylbenzene had a steric hindrance near the six-fold axis of symmetry of the pTT orbitals on both sides of the aromatic plane. This hindrance is evident by the lack of TT-complex formation in the ortho isomer with tetracyano­ ethylene, while the corresponding meta and para isomers form deep colored complexes with this reagent.*® Figure 2 Partially Hindered Faces in O-Dineopentyl- tetramethylbenzene The order of IT donor strength of these three isomeric tetramethyldineopentylbenzenes with respect to iodine was found to be p> m> o. The contrast between the ortho and the meta and para isomers in TT-complex formation with iodine was not dramatic as with tetracyanoethylene.*^ 11. R. E, Lovins, L. J. Andrews, and R. M. Keefer, J. Phys. Chem., 68, 2553 (1964). The preparation of the similar l,2,5-trimethyl-3,4- dineopentylbenzene and l,3,5-trimethyl-2,4-dineopentylbenzene was undertaken to gain information on U-complexes in certain aromatic nitration and bromination reactions. A major
Recommended publications
  • Fluorinated Butatrienes
    Fluorinated Butatrienes Dissertation zur Erlangung des akademischen Grades des Doktors der Naturwissenschaften (Dr. rer. nat.) eingereicht im Fachbereich Biologie, Chemie, Pharmazie der Freien Universität Berlin vorgelegt von Dipl.-Chem. Christian Ehm aus Berlin Berlin, April 2010 1. Gutachter: Prof. Dr. Dieter Lentz 2. Gutachter: Prof. Dr. Beate Paulus Disputation am 28.6.2010 I Acknowledgements It would not have been possible to write this doctoral thesis without the help and support of the kind people around me, to only some of whom it is possible to give particular mention here. First and foremost I would like to thank my principal supervisor, Professor Dieter Lentz, for the opportunity of doing research in his group. Without his continuous support and encouragement this thesis would not be in the present state. I highly appreciate that Professor Beate Paulus has agreed to be co-referee of my thesis. I would like to cordially thank Lada for her love and patience as well as her interest in my research. Special thanks to my family for their continuous support and love. I would like to thank Mike Roland, Sten Dathe and Sven Wünsche for their friendship and the fun we have had every Sunday evening. Special thanks to Sebastian Freitag, Boris Bolsinger and Frederic Heinrich for their friendship. They deserve much gratefulness for keeping me on the right way. I would like to thank all my colleagues at the Institut für Chemie und Biochemie, Abteilung Anorganische Chemie. In particular I want to thank all members of the Lentz group, Thomas Hügle, Moritz Kühnel, Dr. Floris Akkerman, Dr.
    [Show full text]
  • United States Patent Office Patented Apr
    3,657,317 United States Patent Office Patented Apr. 18, 1972 2 3,657,317 EI 1,3-FUNCTIONALLY DISUBSTITUTED BECYCLOBUTANES rx'A/N - Charles Eugene Coffey, Brandywood, Wilmington, Del, assignor to E. I. du Pont de Nemours and Company, LX. Wilmington, Dei. wherein R, R2, R3, R4, and Rs are as defined above. The No Drawing. Filed June 5, 1967, Ser. No. 643,339 term "lower,' when used in the definitions, denotes a car Int. C. CO7c 61/12, 69/74 bon length of 1-6 carbon atoms. U.S. C. 260-468 B 13 Claims This invention also provides certain novel intermediate 10 compounds of the above process having the general for ABSTRACT OF THE DESCLOSURE mula This invention relates to 1.3-functionally disubstituted R. H. bicyclobutanes, to a process for their manufacture, and to CHNO homopolymers obtainable therefrom. 15 CN ^ 4 OE R. R. BACKGROUND OF THE INVENTION wherein R3, R4, and Rs are defined as above. Recent interest in substituted bicyclobutanes has been DESCRIPTION OF THE PREFERRED stimulated by the discovery of their utility as intermedi 20 EMBODIMENTS ates and additives in the manufacture of various polyesters The starting material for the process of the instant and polyamides. Research in this field has disclosed vari invention is selected from compounds of the general ous substituted bicyclic compounds including some having formula: functional substituent groups. While functionally disubsti tuted bicyclobutane compounds have also been disclosed, 25 R. H. the particular 1,3-functionally disubstituted compounds wherein functional groups are attached at both bridge head carbon atoms have been heretofore unknown.
    [Show full text]
  • STEROID DIALKYLCARBENE REACTIONS Abstract Approved: Dr
    AN ABSTRACT OF THE THESIS OF DALE DAVID DIXON for the DOCTOR OF PHILOSOPHY (Name) (Degree) in "CHEMISTRY (ORGANIC)" presented on\--Wicl j 1(1Wi (Major) (Date) T itle: STEROID DIALKYLCARBENE REACTIONS Abstract approved: Dr. F. T. Bond Steroid carbenes have been investigated as synthetic inter- mediates. Basic decomposition of 4-en-3-one tosylhydrazones (and other A-ring systems) gives varying amounts of 2, 4-dienes, and solvent derived products with diglyme, heptane, tetrachloroethylene, carbon tetrachloride, benzene and cyclohexene. A method for separating complex product mixtures was developed and a study of the effect of reaction conditions carried out. Butyl lithium decom- position gives a high yield of the homoannular diene. Sterically hindered carbenes give only intramolecular products. Saturated steroid carbenes have been shown to give widely varying y Ií insertion ratios. Decomposition of cholestan -3 -one tosylhydrazone in tetrachloroethylene results in the formation of a solvent derieved pyrazoline. The possible role of pyrazolines in other carbene reactions is discussed, A facile route to interesting fused ring pyrazoles has been developed in the l6-en-20-one tosylhydrazone system. With a 16- methyl system the pyrazolenine was isolated and investigated. The 'possible biological properties of these compounds are discussed. Steroid Dialkylcarbene Reactions by Dale David Dixon 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 / / 1 6 S Typed by Gwendolyn Hansen for Dale David Dixon ACKNOWLEDGEMENTS I wish to express my appreciation to Dr.
    [Show full text]
  • Preparation and 13C NMR Investigation of 1,1-Dilithioalkenes
    Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1990 Preparation and 13C NMR investigation of 1,1-dilithioalkenes, 1,2-dilithioalkenes, 1-lithiocyclopropenes and 1,2-dilithiocyclopropenes Hon-Wah Man Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Man, Hon-Wah, "Preparation and 13C NMR investigation of 1,1-dilithioalkenes, 1,2-dilithioalkenes, 1-lithiocyclopropenes and 1,2-dilithiocyclopropenes " (1990). Retrospective Theses and Dissertations. 9860. https://lib.dr.iastate.edu/rtd/9860 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. MICROFILMED 1991 INFORMATION TO USERS The most advanced technology has been used to photograph and reproduce this manuscript 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.
    [Show full text]
  • WO 2017/165822 Al 28 September 2017 (28.09.2017) P O P C T
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2017/165822 Al 28 September 2017 (28.09.2017) P O P C T (51) International Patent Classification: Keita [US/US]; Department of Chemistry, Chevron Sci C07D 295/185 (2006.01) Λ 61Κ 31/495 (2006.01) ence Center (1301 CHVRN), 219 Parkman Avenue, Pitts C07D 403/04 (2006.01) A61K 31/496 (2006.01) burgh, PA 15260 (US). MILLIGAN, John [US/US]; De C07D 413/12 (2006.01) A61K 31/42 (2006.01) partment of Chemistry, Chevron Science Center (1301 C07D 451/02 (2006.01) A61K 31/445 (2006.01) CHVRN), 2 19 Parkman Avenue, Pittsburgh, PA 15260 C07D 409/08 (2006.01) A61K 31/46 (2006.01) (US). C07D 407/04' (2006.01) A61K 31/498 (2006.01) (72) Inventors: WIPF, Peter; Department of Chemistry, Chev C07D 403/06 (2006.01) A61K 31/12 (2006.01) ron Science Center (1301 CHVRN), 219 Parkman Avenue, C07D 401/08 (2006.01) A61K 31/407 (2006.01) Pittsburgh, PA 15260 (US). JOHNSON, James, K.; De C07D 405/06 (2006.01) A61K 31/435 (2006.01) partment of Chemistry, Chevron Science Center (1301 C07D 487/04 (2006.01) A61K 31/47 (2006.01) CHVRN), 2 19 Parkman Avenue, Pittsburgh, PA 15260 C07D 217/16 (2006.01) A61P 35/00 (2006.01) (US). SKODA, Erin, M.; 8913 Early April Way Apt G, C07C 49/563 (2006.01) Columbia, MD 21046 (US). NELSON, Joel, B.; UPMC, (21) International Application Number: 200 Lothrop St., Pittsburgh, PA 15213-2582 (US).
    [Show full text]
  • 1 a Theoretical Stereoselectivity Model of Photochemical
    A Theoretical Stereoselectivity Model of Photochemical Denitrogenations of Diazoalkanes Towards Strained 1,3-Dihalogenated Bicyclobutanes Jingbai Li, Rachel Stein, and Steven A. Lopez* Department of Chemistry & Chemical Biology, Northeastern University, 360 Huntington Ave, Boston MA, 02115 Abstract Photochemical reactions exemplify ‘green’ chemistry and are essential for synthesizing highly strained molecules with mild conditions with light. The light-promoted denitrogenation of bicyclic azoalkanes affords functionalized, stereoenriched bicyclo[1.1.0]butanes. We revisited these reactions with multireference calculations and non-adiabatic molecular dynamics (NAMD) simulations for a series of diazabicyclo[2.1.1]hexenes to predict the photophysics, reactivities, and stereoselectivities. We used complete active space self-consistent field (CASSCF) calculations with an (8,8) active space and ANO-S-VDZP basis set; the CASSCF energies were corrected with CASPT2(8,8)/ANO-S-VDZP. The excitation is consistently n→π* and ranges from 3.77–3.91 eV for the diazabicyclo[2.1.1]hexenes. Minimum energy path calculations showed stepwise C–N bond breaking and led to a minimum energy crossing point, which favors the stereochemical ‘double inversion’ bicyclobutane product. Wigner sampling of 1 provided Franck- Condon points for 692 NAMD trajectories. We identified competing complete stereoselective and stereochemical scrambling pathways. The stereoselective pathways feature concerted bicyclobutane inversion and N2 extrusion. The stereochemical scrambling pathways involve N2 extrusion followed by bicyclobutane planarization, leading to non-stereoselective outcomes. The predicted diastereomeric excess almost exactly match experiment (calc.d.e.=46% vs. exp.d.e.=47%). Our NAMD simulations with 672, 568, and 596 trajectories for 1-F, 1-Cl, and 1- Br predicted diastereomeric excess (d.e.) of 94–97% for the double inversion products.
    [Show full text]
  • Journal of the American Chemical Society
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 0 Copyright 1986 by the American Chemical Society VOLUME108, NUMBER4 FEBRUARY19, 1986 Long Interbridgehead Bonds in Acceptor-Substituted Bicyclobutanes Peter H. M. Budzelaar,+" Elfi Kraka,lb Dieter Cremer,lb and Paul von Ragu6 Schleyer*" Contribution from the Institut fur Organische Chemie der Uniuersitat Erlangen- Niirnberg. 0-8520 Erlangen, West Germany, and the Institut fur Organische Chemie der Uniuersitat Koln. 0-5000Koln 41, West Germany. Received July 31, 1985 Abstract: The structures of bicyclobutane 4 and its dimethylene, diimino, and dioxo derivatives 5-7 as well as those of diboretene 8 and diaminodiboretene 9 were determined by ab initio MO theory at the RHF and GVB levels with use of the split-valence 3-21G basis set. The substituted cyclopropanes and cyclopropenes 10-21 were studied for comparison. Bicyclobutane itself has a short C( 1)-C(3) bond between the bridgeheads; the introduction of doubly bound =CH2, =NH, or =O groups at C(2) and C(4) results in a progressive opening of the C(l)-C(3) bond which acquires more ?r character. In bicyclobutane, planarization to the DZhstructure 4b produces a biradicaloid species. The planar molecules 5b-9b have much less biradical character, and 7&9b are aromatic species rather than biradicals. All molecules prefer nonplanar structures, but the planarization energies for 5-9 are very small at the GVB level, indicating easy inversion. Bicyclobutanedione 7, cyclopropenone 13, the diboretenes 8 and 9,and borirenes 14 and 15 exhibit the large stabilization associated with aromatic molecules; dimethylenebicyclobutane 5 and methylenecyclopropene11 are not aromatic.
    [Show full text]
  • University Microfilms, Inc., Ann Arbor, Michigan ADDITION of ELECTRON-DEFICIENT CARBON-CARBON
    This dissertation has been mlcrolUmed exactly as received 6 9-15,953 RICHMOND, Gary Donald, 1942- ADDITION OF ELECTRON-DEFICIENT CARBON- CARBON MULTIPLE BONDS TO STRAINED POLYCYCLIC HYDROCARBONS; THE CHEMICAL AND PHYSICAL PROPERTIES OF fi -KETO SULFOXIDES. The Ohio State University, Ph.D., 1969 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan ADDITION OF ELECTRON-DEFICIENT CARBON-CARBON MULTIPLE BONDS TO STRAINED POLYCYCLIC HYDROCARBONS; THE CHEMICAL AND PHYSICAL PROPERTIES OF P-KETO SULFOXIDES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Gary Donald Richmond, B.A. ■JHHBHHJ- The Olio State University 1968 Approved by Adviser Department of Chemistry ACKNOWLEDGMENTS The author wishes to express his appreciation to Professor Paul G. Gassman for his guidance, assisteince, and personal influence throughout the course of this work. 11 VITA April 6, 19^2 Washington, Pennsylvania 1964 B.A. Washington and Jefferson College, Washington, Pennsylvania September, 1964 Entered the Graduate School of The Ohio State University 1965-1968 National Institutes of Health Predoctoral Fellow PUBLICATIONS The Alkylation of P-Keto Sulfoxides. A General Route to Ketones, J. Org. Chem., 2555 (1966). Backside Attack on Bent Sigma Bonds, J. Am. Chem. Soc., go, 5657 (1968). FIELD OF STUDY Major Field: Organic Chemistry iii COiraEKTS Page ACKNOWIEDGÏŒNTS..................................... il VITA ................................................ iii TABLES............................... ix PART OME. ADDITION OF ELECTRON-DEFICIENT CARBON- CARBON MULTIPLE BONDS TO STRAINED POLY­ CYCLIC HYDROCARBONS ....................... 1 I. Introduction and Historical Review ........... 1 II. Results.................................... 13 A. Tricyclo[U.1.0.0^’^heptane .............. 13 1. Preparation......................... 13 2. Reactions .....
    [Show full text]
  • SOME SYNTHETIC EFFORTS in SMALL RING CHEMISTRY Abstract Approved: F
    AN ABSTRACT OF THE THESIS OF LUKE KWOK TUNG LAM for the M. S. (Degree) in Chemistry presented on (Major) ?14(1 /9(77 Title: SOME SYNTHETIC EFFORTS IN SMALL RING CHEMISTRY Abstract approved: F. Thomas Bond Cyclopropylcyclobutene was prepared via the intermediate dicyclopropylcarbinyl carbene which was generated by the thermal decomposition of the sodium salt of dicyclopropylketone p- toluene- sulfonylhydrazone. The successive thermal isomerization of cyclo- propylcyclobutene to 2- cyclopropyl -1, 3- butadiene and to vinylcyclo- pentene was studied. Kinetic data were obtained for the cyclopropyl- cyclobutene to 2- cyclopropyl -1, 3- butadiene isomerization in the gas phase. Decomposition of the sodium salt was studied in different solvent systems at 130°, but bicyclo(1. 1. 0)butane ring formation was not a major reaction pathway under conditions similar to those used in the decomposition of cyclopropylcarboxaldehyde p- toluene- sulfonylhydrazone. Attempts to synthesize the compounds bicyclo- (2..2.0)hex- 1(4) -ene and bicyclo(2.2.0)hex -1 -ene via carbenoid inter- mediates were hampered by difficulties in preparing the necessary precursors. Some Synthetic Efforts in Small Ring Chemistry by Luke Kwok Tung Lam A THESIS submitted to Oregon State University in partial fulfillment of the requirements for the degree of Master of Science 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 JAf 7. 1(7 Typed by Opal Grossnicklaus for Luke Kwok Tung Lam ACKNOWLEDGEMENT The author wishes to express appreciation to Dr. F. Thomas Bond for his continued interest and patient guidance throughout this investigation and for his critical reading of this manuscript.
    [Show full text]
  • Enzymatic Synthesis of a Bicyclobutane Fatty Acid by a Hemoprotein–Lipoxygenase Fusion Protein from the Cyanobacterium Anabaena PCC 7120
    Enzymatic synthesis of a bicyclobutane fatty acid by a hemoprotein–lipoxygenase fusion protein from the cyanobacterium Anabaena PCC 7120 Claus Schneider*, Katrin Niisuke*, William E. Boeglin*, Markus Voehler†, Donald F. Stec†, Ned A. Porter†, and Alan R. Brash*‡ Departments of *Pharmacology and †Chemistry, Vanderbilt Institute of Chemical Biology, Vanderbilt University School of Medicine, Nashville, TN 37232 Edited by Judith P. Klinman, University of California, Berkeley, CA, and approved October 5, 2007 (received for review July 30, 2007) Biological transformations of polyunsaturated fatty acids often that the catalase-related allene oxide synthase (AOS) is proto- lead to chemically unstable products, such as the prostaglandin typical of an enzyme family that also has diversified functions. endoperoxides and leukotriene A4 epoxide of mammalian biology Accordingly, the unusual catalytic activity of the catalase-related and the allene epoxides of plants. Here, we report on the enzy- coral AOS provided the impetus for the present investigation, matic production of a fatty acid containing a highly strained bicyclic namely to explore other possible occurrences of catalase-related four-carbon ring, a moiety known previously only as a model proteins with novel functions in the biotransformation of poly- compound for mechanistic studies in chemistry. Starting from unsaturated fatty acids. linolenic acid (C18.3␻3), a dual function protein from the cyanobac- By using BLAST searches for sequences similar to the coral terium Anabaena PCC 7120 forms 9R-hydroperoxy-C18.3␻3ina catalase-related domain, one of the top matching hits besides lipoxygenase domain, then a catalase-related domain converts the other coral homologues was identified in the cyanobacterium 9R-hydroperoxide to two unstable allylic epoxides.
    [Show full text]
  • A Computational Toolkit to Understand Orbital Overlap And
    A COMPUTATIONAL TOOLKIT TO UNDERSTAND ORBITAL OVERLAP AND CHEMICAL REACTIVITY by ARSHAD MEHMOOD M.Sc. Chemistry, 2009 The Islamia University of Bahawalpur, Pakistan M.Phil. Physical Chemistry, 2011 The Islamia University of Bahawalpur, Pakistan Submitted to the Graduate Faculty of the College of Science and Engineering Texas Christian University in partial fulfillment of the requirements for the degree of Doctor of Philosophy December 2020 Acknowledgments I am grateful to my advisor, Dr. Benjamin G. Janesko, for his support, motivation, and guidance throughout the years of my Ph.D. Your help in my professional development, personal life, and career planning is exemplary. I am deeply indebted to you for your support in official matters, encouraging me to be independent and supporting me in expanding my skills. I have grown greatly as a researcher and person under your guidance. Thank you for being my mentor and a role model for my future life. I am thankful to the members of my committee, Prof. Jeffery L. Coffer, Prof. Sergei V. Dzyuba, and Prof. Jing Kong (Middle Tennessee State University), for their guidance at each step of my Ph.D. I am also thankful to Prof. Eric E. Simanek and Prof. Kayla N. Green for their help and collaborations. I am grateful to Prof. Onofrio Annunziata and Dr. Yulia V. Sevryugina, for their support and encouragement. Many thanks to my colleague, collaborator, and outrageously talented close friend, Dr. Stephanie I. Jones, who helped me and supported me to succeed during the years of my graduate study at TCU. I am thankful to my friends Dr.
    [Show full text]
  • University Modrilms International 300 N
    NEW CHEMISTRY OF SMALL RING NITRILES Item Type text; Dissertation-Reproduction (electronic) Authors Snider, Scott Christian Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 29/09/2021 06:07:17 Link to Item http://hdl.handle.net/10150/298446 INFORMATION TO USERS This was produced from a copy of a document sent to us for microfilming. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help you understand markings or notations which may appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure you of complete continuity. 2. When an image on the film is obliterated with a round black mark it is an indication that the film inspector noticed either blurred copy because of movement during exposure, or duplicate copy. Unless we meant to delete copyrighted materials that should not have been filmed, you will find a good image of the page in the adjacent frame.
    [Show full text]