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Nuclear Magnetic Resonance Study of Cyclopentenone and Some of Its Derivatives Charles Edward Lyons Iowa State University

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Nuclear Magnetic Resonance Study of Cyclopentenone and Some of Its Derivatives Charles Edward Lyons Iowa State University Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1961 Nuclear magnetic resonance study of cyclopentenone and some of its derivatives Charles Edward Lyons Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Lyons, Charles Edward, "Nuclear magnetic resonance study of cyclopentenone and some of its derivatives " (1961). Retrospective Theses and Dissertations. 1975. https://lib.dr.iastate.edu/rtd/1975 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]. This dissertation has been 62-1359 microfilmed exactly as received LYONS, Charles Edward, 1929- NUCLEAR MAGNETIC RESONANCE STUDY OF CYCLOPENTENONE AND SOME OF ITS DERIVA­ TIVES. Iowa State University of Science and Technology Ph.D., 1961 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan NUCISÂR MACBETIC RESONANCE STUDY OF CTCIJDPENTBNONE AHD SOIE OF ITS DERIVATIVES ty Charles Edward Iyons A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHHCSQPHT Major Subject! Organic Chemistry ApprovedJ Signature was redacted for privacy. Signature was redacted for privacy. Signature was redacted for privacy. Iowa State University Of Science and Technology Ames, Iowa 1961 ii TABIE OF CONTENTS Page INTRODUCTION 1 HISTORICAL 2 DISCUSSION 12 SPECTRA 61 EXPERIMENTAL 91 SUMMAHT 96 ACKNOWIEDGEMBNTS 97 APPENDIX 98 1 INTRODUCTION During the past several years progress has been made in exploring the oheaLstiy of eyclopentenone and soma of its derivatives. This *>rt has led to the preparation of several new compounds and simpler synthetic routes to others. The advent of nuclear magnetic resonance spectrometry and the recent commercial availability of nja.r. spectrometers presented the opportunity to examine these interesting compounds with a powerful new research tool. Thus this study was undertaken with the object of obtaining the NMR spectra of many of the more recently synthesized oyolopentenone deriva­ tives. No spectra of these compounds have previously been reported in the literature. The object of this study was not only to add to the growing body of NMR spectra of organic compounds, but also to confirm previous structure assignments and to observe interesting aspects of NMR spectroscopy as evidenced in the cyclopentenones. 2 HISTORICAL Theory of Nuclear Magnetic Resonance Spectroscopy Nuclear magnetic resonance (HMR) was first observed in bulk matter 1 2 in 1945. ' The first spectra with separate lines for chemically different nuclei in the same molecule were obtained for alcohols by Arnold and co-workers^ in 1951* In the succeeding decade NMR techniques have rapidly advanced and wide applications to organic chemistry have been made. Jl c Many treatments of NMR theory exist in the literature, ' conse­ quently only a brief review of the theory will be undertaken here. The nuclei of certain isotopes behave as if they were charged spinning bodies. This circulation of charge produces a magnetic moment along the axis of rotation. Certain of these isotopes are of particular interest in organic chemistry, e.g. ^3c, and 31p. They are considered to have nuclear spin I of This means that the magnitude of their magnetic moments in any given direction has only two equal, bat M. Puree11, H. C. Torrey and R. V. Pound, Phvs. Rev.. 69. 37 (1946). Bloch, W. W. Hansen and M. Packard, Phvs. Rev.. 69. 127 (1946). ^J. T. Arnold, S. S. Dharmatti and M. E. Packard, j,. Chem. Phvs.. 12. 507 (1951). %or leading references to the early literature see J. E. Hertz, Chea. Rev».. H, 829 (1955). 5A recent comprehensive treatment of HMR theory may be found in J. A. Pople, W. 0. Schneider and H. J. Bernstein, Higk-Resolution Nuclear Magnetic Resonance, New Tork, N.T., McGraw-Hill Book Co., Inc., 1959* 3 opposite. Ouôdirvatsle values that correspond to spin quantun numbers equal to +§• and If an external magnetic field is applied to a group of these nuclei, these nuclear nagnets will experience torques and will tend to line up with the field (I = -\) or against the field (I = +§•). The more favorable energy state is the one corresponding to alignment with the field. The difference in energy between the states, AB, is proportional to the strength of the applied field H at the nucleus. At ordinary temperatures within the practically attainable range of values for H, the equilibrium concentrations of nuclei in the two possible states are always very nearly equal. This is because the energy differences between the states are quite small and because alignment of the nuclei with the field is opposed by thermal agitation in accord with the Boltzmann distribution law. It has been calculated^ that at 300°K in a field of 9tkG0 gauss that the ratio is 1.0000066/1 in favor of the spin state 1 * When a nucleus with a magnetic montent is acted upon by a magnetic field its magnetic vector behaves as if it were undergoing precession around the field axis at an angular velocity that is proportional to the magnetic field at the nucleus and is exactly equal to the frequency of electromagnetic radiation which is necessary to induce a transition from one nuclear spin state to an adjacent level. To summarize, under appropriate conditions these nuclei can absorb . D. Roberts, Nuclear Magnetic Resonance, New York, N.Y., McGraw- Hill Book Co., Inc., 1959» p. 9» 4 energy froz a magnetic field, in a direction at right angles to the main field, oscilia, ting with a frequency in the radio-frequency region to cause transitions between adjacent energy levels. Such absorption gives rise to what is termed the nuclear magnetic resonance spectrum. A nucleus in an upper spin state returns to a lower state fcy naari.i of radiationless transitions of energy to a neighboring nucleus or to the entire molecular system. These energy dissipation processes are termed relaxation processes. The local magnetic field near a particular nucleus is to a small degree dependent on its molecular environment. This is because the extranuclear electrons magnetically screen the nucleus so that the mag­ netic field felt by the nucleus is not quite the same as the applied field. The observed resonance frequency of a given nucleus is thus a very sensitive function of this molecular environment. Experimental Method An NMR spectrometer consists essentially of four parts: (1) a magnet capable of producing a very strong, highly homogeneous field, (2) a means of continuously varying the magnetic field over a very small range, (3) a radio-frequency oscillator, and (4) a radio-frequency receiver. A large magnetic field is directed along the e-axis, and the alternating magnetic field produced by the oscillator is directed along the x-axis. The receiver coil is oriented so as to respond to an alternating magnetic field along the y-axis. Thus the oscillator must 5 induce a component of y-aagnetization in the saaple if a signal is to be picked up by the receiver. Experimentally one changes the precession frequency of the nuclei by varying the applied magnetic field while the oscillator frequency is kept constant. At some value of the field the nuclear precession frequency becomes equal to the frequency of the rotating field vector produced by the oscillator and the energy may then be transferred from the oscillator to the nuclei, causing some of them to go to the higher energy state with I = +§•. At the same time the rotating vield vector acts to tip the vectors of the individual nuclear magnets, with which it is 90° out of phase, away from the field axis and thus causes the axis of the cone of vectors to rotate around the field axis at the precession frequency. This has the result of producing a rotating component of magnetization in the x and y directions which processes around the field axis with the same angular velocity as the individual nuclei. This alternating field in the y-direction induces a current in the receiver coil and generates an NMR signal. As the magnetic field is further increased the nuclei drop out of phase with the rotating field vector. As the y-magnetization decreases the signal dies away in the receiver. Conventions and Terminology Ch^njç^l shj# Differences in absorption line positions for nuclei of the same kind, but located in different molecular environments, are called chemical shifts. Chemical shifts have their origin in diaaagnetic and 6 paramagnetic shielding effects produced by circulation of both bonding and non-bonding electrons in the neighborhood of the nuclei. These effects are proportional to the applied field. The magnitude of a given chemical shift is usually taken with refer­ ence to a standard. Tetramethylsilane (TIB) is widely used as an "internal standard." A very small amount of T)G is mixed with the sample to provide an internal proton reference line. SpiD-gpjn rsrnpl^-nfl Spin-spin coupling usually manifests itself as fine structure in main absorption peaks. It is explained by the fact that the field ex­ perienced by the protons of one group is influenced by the spins of protons in the neighboring group. In a saturated system proton spin coupling is usually negligible over more than three bonds. Coupling is independent of the applied field because it arises from fixed increments in the total magnetic field produced at a given nucleus by the magnetic moments of neighboring nuclei and is transmitted by the bonding electrons. Spin.spin coupling is expressed in cycles per second (cps) and denoted by the coupling constant J.
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