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Nuclear Magnetic Resonance Applications to Organic Chemistry.pdf

October 26, 2009 · Filed Under Chemistry  · Tags: , , , ,

Taken from the Preface: This brief book is the outgrowth of some forty lectures in which it was attempted to explain the phenomenon of nuclear magnetic resonance absorption and the uses of high-resolution nuclear magnetic resonance spectroscopy to organic chemists whose background, like that of the author, has often been deficient in nuclear and electromagnetic theory. Quite a number of suggestions were received for presentation of the material in printed form with illustrations based on the lecture slides. This has now been done, and it is hoped that the result will be of service to practicing chemists and students as a guide to various applications of NMR spectroscopy and an introduction to more authoritative works. Throughout, the coverage is illustrative rather than comprehensive. The author apologizes for choosing rather too many examples of applications from his own research, but it is always easiest to write about what one knows best. He is greatly indebted to Dr. W. D. Phillips of the E. I. du Pont Company for helping to kindle his interest in NMR research and to Dr. James N. Shoolery of Varian Associates and Professors V. Schomaker and H. M. McConnell for many patient hours of explanation with respect to both simple and difficult points of theory. The Office of Naval Research supported much of the research described herein which was carried out at the California Institute of Technology. Dr. Shoolery kindly supplied material for several of the figures, and Dr. Marjorie C. Caserio helped greatly with many of the details in getting the book together. Helpful suggestions were received from Professors D. Y. Curtin, R. Breslow, and D. E. Applequist. Professors William S. Johnson and E. E. van Tamelen supplied several unpublished spectra for Chapters 2 and 3. John D. Roberts

Contents:

  • Preface
  • Introduction The Nuclear Resonance Phenomenon
    • Introduction
    • Nuclear Magnetic Resonance Spectrometers
    • Magnetic Properties of Nuclei Nuclear Spin
    • Magnetic Quantum Numbers
    • Nuclear Precession
    • Nuclear Relaxation
    • Longitudinal Relaxation, TI
    • Transverse Relaxation, T ,
    • The Nuclear Resonance Signal
    • Relaxation Effects on NMR Signals
    • Properties of Magnetic Nuclei of Interest to Organic Problems
  • The Chemical Shift
    • Introduction The Chemical-shift Parameter
    • Measurement of Chemical Shift
    • Some Factors Which Influence 6
    • Chemical Shifts for Other Nuclei
    • Proton 6 Values and Electronegativity
    • 6 and Hammett’s a Constants
    • Resonance Signal Areas and Widths
    • Chemical Shifts and Organic Structure Determinations General Considerations
    • Illustrative Analysis of a Reaction Product
    • Accentuation of Chemical Shifts by Paramagnetic Salts
  • Spin-Spin Splitting
    • The High-resolution Ethanol Spectrum
    • Spin-Spin Splitting in a Single Crystal
    • Spin-Spin Splitting in Liquids
    • Spin-Spin Splitting in the Ethyl Group
    • More Complex Spin-Spin Splittings
    • Magnitudes of Coupling Constants
    • Coupling between Equivalent and Nearly Equivalent Protons
    • Spin-Spin Couplings in Rigid Systems
    • Spin-Spin Splitting and Molecular Asymmetry
  • Nuclear Magnetic Resonance and Reaction Kinetics
    • Introduction Proton Exchange in Water-Acetic Acid Mixtures
    • Relationship between Resonance Line Shapes and Exchange Rates
    • Proton Exchange in Ethanol-Water Mixtures
    • Ethyl Acetoacetate and Its En01 Form
    • Rates of Rotation Around 40 - N < Bonds of Amides
    • Restricted Rotation in Ethane Derivatives
    • Nitrogen Inversion Frequencies of Cyclic Imines
    • Proton Exchange in Ammonia and Ammonium Ions
  • Nuclear Quadrupole Relaxation Effects Double Resonance
    • Proton Resonance Line Broadening by N
    • Nuclear Quadrupoles and Quadrupole-induced Relaxation
    • Proton N-K Resonance of Pyrrole Double Resonance
    • Quadrupole-induced Relaxation with Other Nuclei
    • Applications of Double Resonance
  • Appendix A The Bloch Equations
  • Appendix B Bibliography
  • Appendix C Problems
  • Name Index
  • Subject Index

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