Organic Structure Determination Using 2-D NMR Spectroscopy - 2nd Edition - ISBN: 9780123849700, 9780123849717

Organic Structure Determination Using 2-D NMR Spectroscopy

2nd Edition

A Problem-Based Approach

Authors: Jeffrey Simpson
Paperback ISBN: 9780123849700
eBook ISBN: 9780123849717
Imprint: Academic Press
Published Date: 30th December 2011
Page Count: 540
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Organic Structure Determination Using 2-D NMR Spectroscopy: A Problem-Based Approach, Second Edition, is a primary text for a course in two-dimensional (2-D) nuclear magnetic resonance (NMR) techniques, with the goal to learn to identify organic molecular structure. It presents strategies for assigning resonances to known structures and for deducing structures of unknown organic molecules based on their NMR spectra.

The book begins with a discussion of the NMR technique, while subsequent chapters cover instrumental considerations; data collection, processing, and plotting; chemical shifts; symmetry and topicity; through-bond effects; and through-space effects. The book also covers molecular dynamics; strategies for assigning resonances to atoms within a molecule; strategies for elucidating unknown molecular structures; simple and complex assignment problems; and simple and complex unknown problems. Each chapter includes problems that will enable readers to test their understanding of the material discussed. The book contains 30 known and 30 unknown structure determination problems. It also features a supporting website from which instructors can download the structures of the unknowns in selected chapters, digital versions of all figures, and raw data sets for processing.

This book will stand as a single source to which instructors and students can go to obtain a comprehensive compendium of NMR problems of varying difficulty.

Key Features

  • Presents strategies for assigning resonances to known structures and for deducing structures of unknown organic molecules based on their NMR spectra
  • Contains 30 known and 30 unknown structure determination problems
  • Features a supporting website from which instructors can download the structures of the unknowns in selected chapters, digital versions of all figures, and raw data sets for processing


This is a primary text for a course in NMR techniques, with the goal to learn to identify organic molecular structure.

Table of Contents



Preface to the First Edition

Chapter 1. Introduction

1.1. What Is Nuclear Magnetic Resonance?

1.2. Consequences of Nuclear Spin

1.3. Application of a Magnetic Field to a Nuclear Spin

1.4. Application of a Magnetic Field to an Ensemble of Nuclear Spins

1.5. Tipping the Net Magnetization Vector from Equilibrium

1.6. Signal Detection

1.7. The Chemical Shift

1.8. The 1-D NMR Spectrum

1.9. The 2-D NMR Spectrum

1.10. Information Content Available Using NMR Spectroscopy

Chapter 2. Instrumental Considerations

2.1. Sample Preparation

2.2. Locking

2.3. Shimming

2.4. Temperature Regulation

2.5. Modern NMR Instrument Architecture

2.6. Pulse Calibration

2.7. Sample Excitation and the Rotating Frame of Reference

2.8. Pulse Rolloff

2.9. Probe Variations

2.10. Analog Signal Detection

2.11. Signal Digitization

Chapter 3. Data Collection, Processing, and Plotting

3.1. Setting the Spectral Window

3.2. Determining the Optimal Wait (Delay) Between Scans

3.3. Setting the Acquisition Time

3.4. How Many Points to Acquire in a 1-D Spectrum

3.5. Zero Filling and Digital Resolution

3.6. Setting the Number of Points to Acquire in a 2-D Spectrum

3.7. Truncation Error and Apodization

3.8. The Relationship Between T2∗ and Observed Line Width

3.9. Resolution Enhancement

3.10. Forward Linear Prediction

3.11. Pulse Ringdown and Backward Linear Prediction

3.12. Phase Correction

3.13. Baseline Correction

3.14. Integration

3.15. Measurement of Chemical Shifts and J-Couplings

3.16. Data Representation

Chapter 4. 1H and 13C Chemical Shifts

4.1. The Nature of the Chemical Shift

4.2. Aliphatic Hydrocarbons

4.3. Saturated, Cyclic Hydrocarbons

4.4. Olefinic Hydrocarbons

4.5. Acetylenic Hydrocarbons

4.6. Aromatic Hydrocarbons

4.7. Heteroatom Effects

Chapter 5. Symmetry and Topicity

5.1. Homotopicity

5.2. Enantiotopicity

5.3. Diastereotopicity

5.4. Chemical Equivalence

5.5. Magnetic Equivalence

Chapter 6. Through-Bond Effects

6.1. Origin of J-Coupling

6.2. Skewing of the Intensity of Multiplets

6.3. Prediction of First-Order Multiplets

6.4. The Karplus Relationship for Spins Separated by Three Bonds

6.5. The Karplus Relationship for Spins Separated by Two Bonds

6.6. Long Range J-Coupling

6.7. Decoupling Methods

6.8. One-Dimensional Experiments Utilizing J-Couplings

6.9. Two-Dimensional Experiments Utilizing J-Couplings

Chapter 7. Through-Space Effects

7.1. The Dipolar Relaxation Pathway

7.2. The Energetics of an Isolated Heteronuclear Two-Spin System

7.3. The Spectral Density Function

7.4. Decoupling One of the Spins in a Heteronuclear Two-Spin System

7.5. Rapid Relaxation via the Double Quantum Pathway

7.6. A One-Dimensional Experiment Utilizing the NOE

7.7. Two-Dimensional Experiments Utilizing the NOE

Chapter 8. Molecular Dynamics

8.1. Relaxation

8.2. Rapid Chemical Exchange

8.3. Slow Chemical Exchange

8.4. Intermediate Chemical Exchange

8.5. Two-Dimensional Experiments that Show Exchange

Chapter 9. Strategies for Assigning Resonances to Atoms within a Molecule

9.1. Prediction of Chemical Shifts

9.2. Prediction of Integrals and Intensities

9.3. Prediction of 1H Multiplets

9.4. Good Bookkeeping Practices

9.5. Assigning 1H Resonances on the Basis of Chemical Shifts

9.6. Assigning 1H Resonances on the Basis of Multiplicities

9.7. Assigning 1H Resonances on the Basis of the gCOSY Spectrum

9.8. The Best Way to Read a gCOSY Spectrum

9.9. Assigning 13C Resonances on the Basis of Chemical Shifts

9.10. Pairing 1H and 13C Shifts by Using the HSQC/HMQC Spectrum

9.11. Assignment of Nonprotonated 13C's on the Basis of the HMBC Spectrum

Chapter 10. Strategies for Elucidating Unknown Molecular Structures

10.1. Initial Inspection of the One-Dimensional Spectra

10.2. Good Accounting Practices

10.3. Identification of Entry Points

10.4. Completion of Assignments

Chapter 11. Simple Assignment Problems

Problem 11.1. 2-Acetylbutyrolactone in CDCl3 (Sample 26)

Problem 11.2. α-Terpinene in CDCl3 (Sample 28)

Problem 11.3. (1R)-endo-(+)-Fenchyl Alcohol in CDCl3 (Sample 30)

Problem 11.4. (-)-Bornyl Acetate in CDCl3 (Sample 31)

Problem 11.5. N-Acetylhomocysteine Thiolactone in CDCl3 (Sample 35)

Problem 11.6. Guaiazulene in CDCl3 (Sample 52)

Problem 11.7. 2-Hydroxy-3-pinanone in CDCl3 (Sample 76)

Problem 11.8. (R)-(+)-Perillyl Alcohol in CDCl3 (Sample 81)

Problem 11.9. 7-Methoxy-4-methylcoumarin in CDCl3 (Sample 90)

Problem 11.10. Sucrose in D2O (Sample 21)

Chapter 12. Complex Assignment Problems

Problem 12.1. Longifolene in CDCl3 (Sample 48)

Problem 12.2. (+)-Limonene in CDCl3 (Sample 49)

Problem 12.3. L-Cinchonidine in CDCl3 (Sample 53)

Problem 12.4. (3aR)-(+)-Sclareolide in CDCl3 (Sample 54)

Problem 12.5. (-)-Epicatechin in Acetone-d6 (Sample 55)

Problem 12.6. (-)-Eburnamonine in CDCl3 (Sample 71)

Problem 12.7. trans-Myrtanol in CDCl3 (Sample 72/78)

Problem 12.8. cis-Myrtanol in CDCl3 (Sample 73/77)

Problem 12.9. Naringenin in Acetone-d6 (Sample 89)

Problem 12.10. (-)-Ambroxide in CDCl3 (Sample Ambroxide)

Chapter 13. Simple Unknown Problems

Problem 13.1. Unknown 13.1 in CDCl3 (Sample 20)

Problem 13.2. Unknown 13.2 in CDCl3 (Sample 41)

Problem 13.3. Unknown 13.3 in CDCl3 (Sample 22)

Problem 13.4. Unknown 13.4 in CDCl3 (Sample 24)

Problem 13.5. Unknown 13.5 in CDCl3 (Sample 34)

Problem 13.6. Unknown 13.6 in CDCl3 (Sample 36)

Problem 13.7. Unknown 13.7 in CDCl3 (Sample 50)

Problem 13.8. Unknown 13.8 in CDCl3 (Sample 83)

Problem 13.9. Unknown 13.9 in CDCl3 (Sample 82)

Problem 13.10. Unknown 13.10 in CDCl3 (Sample 84)

Chapter 14. Complex Unknown Problems

Problem 14.1. Unknown 14.1 in CDCl3 (Sample 32)

Problem 14.2. Unknown 14.2 in CDCl3 (Sample 33)

Problem 14.3. Unknown 14.3 in CDCl3 (Sample 51)

Problem 14.4. Unknown 14.4 in CDCl3 (Sample 74)

Problem 14.5. Unknown 14.5 in CDCl3 (Sample 75)

Problem 14.6. Unknown 14.6 in CDCl3 (Sample 80)

Problem 14.7. Unknown 14.7 in Acetone-d6 (Sample 86)

Problem 14.8. Unknown 14.8 in CDCl3 (Sample 87)

Problem 14.9. Unknown 14.9 in CDCl3 (Sample 88)

Problem 14.10. Unknown 14.10 in CDCl3 (Sample 72)

Chapter 15. More Assignment Problems

Problem 15.1. α-Cubebene in CDCl3 (Sample 95)

Problem 15.2. (1S∗, 4S∗, 10S∗)-1-Ethyl-4-(hydroxyethyl)quinolizidine in CDCl3 (Sample Courtesy of Shaun Fontaine and Rick Danheiser) (Sample 106)

Problem 15.3. Sinomenine in CDCl3 (Sample 108)

Problem 15.4. Artemisinin in CDCl3 (Sample 109)

Problem 15.5. Vincamine in CDCl3 (Sample 110)

Problem 15.6. Brucine in CDCl3 (Sample 113)

Problem 15.7. Piperine in CDCl3 (Sample 114)

Problem 15.8. Melatonin in DMSO-d6 (Sample 116)

Problem 15.9. Compound 142 in CDCl3 (Sample Courtesy of Jason Cox and Tim Swager) (Sample 142)

Problem 15.10. Compound 119 in CDCl3 (Sample Courtesy of Ryan Moslin and Tim Swager) (Sample 119)

Chapter 16. More Unknown Problems

Problem 16.1. Unknown 16.1 in CDCl3 (Sample 115)

Problem 16.2. Unknown 16.2 in DMSO-d6 (Sample 111)

Problem 16.3. Unknown 16.3 in CDCl3 (Sample 94)

Problem 16.4. Unknown 16.4 in CDCl3 (Sample 104)

Problem 16.5. Unknown 16.5 in DMSO-d6 (Sample 102)

Problem 16.6. Unknown 16.6 in CDCl3 (Sample 97)

Problem 16.7. Unknown 16.7 in CD3OD (Sample 98)

Problem 16.8. Unknown 16.8 in CDCl3 (Sample 99)

Problem 16.9. Unknown 16.9 in CDCl3 (Sample 100)

Problem 16.10. Unknown 16.10 in CDCl3 (Sample 101)

Glossary of Terms



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About the Author

Jeffrey Simpson

Affiliations and Expertise

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA


"I like [the book] a lot. Books that cover theory in depth AND lots of problems are (surprisingly) rare." --Steven M. Graham, St. John's University

"The abundance of problems and highly detailed glossary are especially noteworthy; the quality of the spectrum presentations is excellent [...] Overall organization works well, and the layout and other 'production values' are what one has long come to expect from [Academic Press]." --Barry Shapiro

"When trying to explain two-dimensional nuclear magnetic resonance (NMR) spectroscopy, one may strive to avoid two pitfalls: getting bogged down in the mathematics behind the technique, or skipping the mathematics altogether and by default making the technique a "magic box." In his book, Simpson (MIT) has nearly done the impossible, covering two-dimensional NMR without slipping into either of those problems. Starting off with the instrumental setups and working through topics such as pulse sequences and spectral interpretation, this book gives readers all that they will need to prepare, run, and interpret a 2-D NMR experiment. This work would be useful for anyone who is currently using 2-D NMR and is a must for newcomers to the technique. Simpson provides almost 100 spectra to interpret as exercises, which make this volume an ideal teaching tool for 2-D NMR spectroscopy. Summing Up: Essential. Upper-division undergraduate through professional collections." -- S. S. Mason, Mount Union College writing CHOICE April 2009

"This book achieves what it sets out in its title. It is a balanced text covering both theoretical and practical aspects of NMR spectroscopy. The first seven chapters give a comprehensive discussion of the relevant theories and practical considerations in the use of NMR spectroscopy for organic structure determination. The later chapters delve into strategies for organic structure determination and provide complex and simple assignment and identification problems, representing the most common applications of 2D NMR… I found this book to be very well written and accessible." --Chemistry World