Contents

I Introduction to NMR Spectroscopy . . . . . . . . . . . 1

1.1 Nuclear Magnetism . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Nuclear Precession . . . . . . . . . . . . . . . . . . . . . . . 2
1.3 Nuclear Magnetic Energy Levels . . . . . . . . . . . . . . . . . 3

1.4 Nuclear Magnetic Resonance . . . . . . . . . . . . . . . . . . . 4

1.5 Relaxation . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.5.1 Equilibrium of Nuclear Spins in the B. Field . . . . . . . . . . . . 5
1.5.2 Spin-Lattice Relaxation . . . . . . . . . . . . . . . . . . . . . 5
1.5.3 Spin-Spin Relaxation . . . . . . . . . . . . . . . . . . . . . . 6
1.5.4 Saturation . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.6 Magnetization Vectors . . . . . . . . . . . . . . . . . . . . . . 7

1.7 Bloch Equations . . . . . . . . . . . . . . . . . . . . . . . . 8

1.7.1 Motion of the Magnetization Vector in a Fixed Coordinate System . . 8
1.7.2 Motion of the Magnetization Vector in the Rotating Coordinate System 9
1.7.3 NMR in the Rotating Frame of Reference . . . . . . . . . . . . . 10
1.7.4 Relaxation in the Rotating Frame of Reference . . . . . . . . . . . 12
1.8 NMR Spectra . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.8.1 Nuclear Induction . . . . . . . . . . . . . . . . . . . . . . . . 13
1.8.2 Absorption and Dispersion Spectra . . . . . . . . . . . . . . . . 13
1.8.3 Magnitude Spectra . . . . . . . . . . . . . . . . . . . . . . . 14

1.9 Chemical Shift . . . . . . . . . . . . . . . . . . . . . . . . . 15

1.9.1 Shielding of Nuclei in Atoms and Molecules . . . . . . . . . . . . 15
1.9.2 Calibration of NMR Spectra . . . . . . . . . . . . . . . . . . . 16
1.9.3 Reference Standard . . . . . . . . . . . . . . . . . . . . . . . 17

1.10 Spin-Spin Coupling . . . . . . . . . . . . . . . . . . . . . . . 17

1.10.1 Multiplicity of Signals . . . . . . . . . . . . . . . . . . . . . . 17
1.10.2 Coupling Constants . . . . . . . . . . . . . . . . . . . . . . . 18
 X Contents

1.10.3 Comparison between Chemical Shifts and Coupling Constants . . . . 18

1.10.4 Origin of Spin-Spin Coupling . . . . . . . . . . . . . . . . . . . 18

2 Instrumental Methods of I3C N M R Spectroscopy . . . 21

2.1 Sensitivity of 13C NMR Spectroscopy . . . . . . . . . . . . . . . 21
2.2 Methods of Sensitivity Enhancement in 13C NMR Spectroscopy . . . . 21
2.3 Continuous Wave NMR Spectroscopy . . . . . . . . . . . . . . . 22
2.4 Pulsed NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . 22
2.4.1 Magnetization . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.4.2 90; Pulse . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.4.3 Transverse Magnetization . . . . . . . . . . . . . . . . . . . . 23
2.4.4 Free Induction Decay . . . . . . . . . . . . . . . . . . . . . . 24
2.4.5 Pulse Interferograms . . . . . . . . . . . . . . . . . . . . . . . 25
2.5 Pulse Fourier Transform (PFT) NMR Spectroscopy . . . . . . . . . 28
2.5.1 FID Signal and NMR Spectrum as Fourier Transforms . . . . . . . 28
2.5.2 Position. Width and Phase of FT NMR Signals . . . . . . . . . . . 29
2.5.3 Acquisition of Pulse Interferograms for Fourier Transformation . . . . 30
2.5.3.1 Digitization . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.5.3.2 Dwell Time and Pulse Interval . . . . . . . . . . . . . . . . . . 30
2.5.3.3 Filtering of Frequencies Outside of the Spectral Width . . . . . . . . 30
2.5.4 Optimization of Pulse Interferograms for Fourier Transformation . . . 31
2.5.4.1 Adjustment of Pulse Frequency . . . . . . . . . . . . . . . . . . 31
2.5.4.2 Adjustment of Pulse Width . . . . . . . . . . . . . . . . . . . . 32
2.5.5 Data Transformation and Subsequent Manipulations . . . . . . . . . 33
2.5.5.1 Fourier Transformation . . . . . . . . . . . . . . . . . . . . . 33
2.5.5.2 Phase Correction . . . . . . . . . . . . . . . . . . . . . . . . 33
2.5.5.3 Computation of Magnitude Spectra . . . . . . . . . . . . . . . . 36
2.5.6 Controlling Signal to Noise and Resolution in
PFT NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . . 36
2.5.6.1 Digital Filtering . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.5.6.2 Number of FID Data Points and Digital Resolution . . . . . . . . . 36
2.5.7 Spin-Lattice Relaxation and Signal to Noise in
PFT NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . . 39
2.5.8 Comparison between CW and PFT . . . . . . . . . . . . . . . . 41
2.6 Double Resonance Techniques used in 3C NMR Spectroscopy
as Assignment Aids . . . . . . . . . . . . . . . . . . . . . . . 43
2.6.1 Basic Concept of Spin Decoupling . . . . . . . . . . . . . . . . . 43
2.6.2 Proton Broad Band Decoupling in 13C NMR Spectroscopy . . . . . . 44
2.6.3 Nuclear Overhauser Effect in 13C{'H} NMR Experiments . . . . . . 46
2.6.4 Quenching Nuclear Overhauser Effects in 3C(1H} NMR Experiments 47
2.6.5 Proton Off-Resonance Decoupling . . . . . . . . . . . . . . . . . 47
2.6.6 Pulsed Proton Broadband Decoupling . . . . . . . . . . . . . . . 50
2.6.6.1 Measurement of NOE Enhanced Coupled 13C NMR Spectra . . . . . 50
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2.6.6.2 Measurement of Proton-Decoupled I3C NMR Spectra with

Suppressed NOE . . . . . . . . . . . . . . . . . . . . . . . . 50
2.6.6.3 Measurement of Nuclear Overhauser Enhancements . . . . . . . . . 51
2.6.7 Selective Proton Decoupling . . . . . . . . . . . . . . . . . . . 53
2.7 Measurement of I3C Relaxation Times . . . . . . . . . . . . . . . 55
2.7.1 Spin-Lattice Relaxation Times . . . . . . . . . . . . . . . . . . 55
2.7.1.1 ..
Inversion-Recovery or 180 z. 90 Method . .
Saturation-Recovery Method . . . . . . . .
. . . . . . . . . . . 55
2.7.1.2 . . . . . . . . . . . 59
2.7.1.3 ..
Progressive Saturation or 90 z.... Method . .
Spin-Spin Relaxation Times . . . . . . . .
. . . . . . . . . . . 60
. . . . . . . . . . . 63
2.7.2
2.7.2.1 CPMGSE Experiments . . . . . . . . . . . . . . . . . . . . . 63
2.7.2.2 Spin-Locking Fourier Transform Experiments . . . . . . . . . . . . 66
2.8 Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . 67
2.8.1 Magnet . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
2.8.2 Stabilization Channel (Lock) . . . . . . . . . . . . . . . . . . . 70
2.8.3 Observation Channel . . . . . . . . . . . . . . . . . . . . . . 71
2.8.4 Decoupling Channel . . . . . . . . . . . . . . . . . . . . . . . 71
2.8.5 Sample . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.9 From the First to the Second Dimension of I3C NMR Spectroscopy . . 73
2.9.1 The Spin-Echo . . . . . . . . . . . . . . . . . . . . . . . . . 73
2.9.2 J-Modulated Spin-Echo . . . . . . . . . . . . . . . . . . . . . 75
2.9.3 Polarization Transfer . . . . . . . . . . . . . . . . . . . . . . 78
2.9.3.1 Selective Polarization Transfer . . . . . . . . . . . . . . . . . . 79
2.9.3.2 Non-Selective Polarization Transfer . . . . . . . . . . . . . . . . 80
2.9.4 Measurement of Carbon-Carbon Coupling Constants Without
13C Enrichment: INADEQUATE . . . . . . . . . . . . . . . . . 84
2.10 The Second Dimension . . . . . . . . . . . . . . . . . . . . . 87
2.10.1 Basic Concept . . . . . . . . . . . . . . . . . . . . . . . . . 87
2.10.2 J-Resolved Two-Dimensional 13C NMR Spectra . . . . . . . . . . 89
2.10.3 Two-Dimensional Carbon-Proton Shift Correlation . . . . . . . . . 92
2.10.4

2.10.5

2.10.6
Two-Dimensional .. - C.H. Correlation .
Two-Dimensional Proton-Proton Shift Correlation :
The COSY Experiment . . . . . . . . . . . . . . . . . . . . .

The RELAY Experiment . . . . . . . . . . . . . . . . . . . . .

Two-Dimensional Carbon-Carbon Shift Correlation :
96

100

The Second Dimension of the INADEQUATE Experiment . . . . . . 102

2.10.7 Carbon-13 NMR Spectroscopy: Strategy for Structure Elucidation . . . 104

3 I3C N M R Spectral Parameters and

Structural Properties . . . . . . . . . . . . . . . . . . . . 107
3.1 Chemical Shifts . . . . . . . . . . . . . . . . . . . . . . . . . 107
3.1.1 Comparison of I3C and 'H Shifts . . . . . . . . . . . . . . . . . 107
3.1.2 Referencing I3C Chemical Shifts . . . . . . . . . . . . . . . . . 108
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3.1.3 Survey of 13C Chemical Shifts . . . . . . . . . . . . . . . . . . 110

3.1.3.1 Carbon Hybridization . . . . . . . . . . . . . . . . . . . . . . 111
3.1.3.2 Electronegativity . . . . . . . . . . . . . . . . . . . . . . . . 111
3.1.3.3 Crowding of Alkyl Groups and Substituents . . . . . . . . . . . . 112
3.1.3.4 Unshared Electron Pairs at Carbon . . . . . . . . . . . . . . . . 112
3.1.3.5 Electron Deficiency at Carbon . . . . . . . . . . . . . . . . . . 113
3.1.3.6 Mesomeric Effects. . . . . . . . . . . . . . . . . . . . . . . . 113
3.1.3.7 Conjugation . . . . . . . . . . . . . . . . . . . . . . . . . . 114
3.1.3.8 Steric Interactions . . . . . . . . . . . . . . . . . . . . . . . . 115
3.1.3.9 Electric Fields of Charged Substituents . . . . . . . . . . . . . . . 116
3.1.3.10 Anisotropic Intramolecular Magnetic Fields . . . . . . . . . . . . 116
3.1.3.11 Heavy Atoms . . . . . . . . . . . . . . . . . . . . . . . . . . 117
3.1.3.12 Isotope Effect . . . . . . . . . . . . . . . . . . . . . . . . . 117
3.1.3.1 3 Intramolecular Hydrogen Bonding . . . . . . . . . . . . . . . . . 117
3.1.3.14 Substituent Increments and Functional Group Shifts . . . . . . . . . 118
3.1.4 Medium Shifts . . . . . . . . . . . . . . . . . . . . . . . . . 120
3.1.4.1 Dilution Shifts . . . . . . . . . . . . . . . . . . . . . . . . . 120
3.1.4.2 Solvent Shifts . . . . . . . . . . . . . . . . . . . . . . . . . . 120
3.1.4.3 pH Shifts . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
3.1.5 Isotropic Shifts . . . . . . . . . . . . . . . . . . . . . . . . . 123
3.1.6 Intramolecular Mobility and Temperature Dependence of
13C Chemical Shifts and Line Widths . . . . . . . . . . . . . . . 127
3.1.6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . 127
3.1.6.2 Temperature Dependence of 13C NMR Spectra . . . . . . . . . . . 131
3.2 I3C Coupling Constants . . . . . . . . . . . . . . . . . . . . . 133
3.2.1 Basic Theoretical Considerations . . . . . . . . . . . . . . . . . 133
3.2.2 Carbon-Proton Coupling . . . . . . . . . . . . . . . . . . . . . 134
3.2.2.1 One-Bond Coupling (AH) . . . . . . . . . . . . . . . . . . . . 134
3.2.2.2 Longer-Range Carbon-Proton Couplings: The J C H / J H H Ratio . . . . . 140
3.2.2.3 Two-Bond Coupling (2JcH). . . . . . . . . . . . . . . . . . . . 141
3.2.2.4 Three-Bond Coupling (3JCH) . . . . . . . . . . . . . . . . . . . 143
3.2.3 Carbon-Deuterium Coupling . . . . . . . . . . . . . . . . . . . 147
3.2.4 Carbon-Carbon Coupling . . . . . . . . . . . . . . . . . . . . 147
3.2.4.1 One-Bond Coupling (Jcc). . . . . . . . . . . . . . . . . . . . . 147
3.2.4.2 Longer-Range Carbon-Carbon Couplings (2Jcc, 3Jcc) . . . . . . . . 152
3.2.5 13C- 15N Coupling Constants . . . . . . . . . . . . . . . . . . 155
3.2.5.1 One-Bond Couplings (JCN). . . . . . . . . . . . . . . . . . . . 155
3.2.5.2 Longer-Range Couplings ( 2 ~ C N , 3JCN) . . . . . . . . . . . . . . . 157
3.2.6 Coupling between Carbon and Other Heteronuclei X (X =+ C. H. D) . . 160
3.3 Spin-Lattice Relaxation Times . . . . . . . . . . . . . . . . . . 163
3.3.1 Mechanisms of I3C Spin-Lattice Relaxation . . . . . . . . . . . . 163
3.3.1.1 Relaxation Resulting from Chemical Shift Anisotropy
(CSA Mechanism) . . . . . . . . . . . . . . . . . . . . . . . . 163
3.3.1.2 Relaxation by Scalar Coupling (SC Mechanism) . . . . . . . . . . . 163
3.3.1.3 Relaxation by Spin Rotation (SR Mechanism) . . . . . . . . . . . 163
 Contents XI11

3.3.1.4 Relaxation by Internuclear Dipole-Dipole Interaction

(DD Mechanism) . . . . . . . . . . . . . . . . . . . . . . . . 164
3.3.1.5 Electron Spin-Nucleus Interactions and Consequences . . . . . . . 165 .
3.3.2 Influence of Molecular Motion on Dipole-Dipole Relaxation . . . . 166 .
3.3.3 Information Content of 13C Spin-Lattice Relaxation Times . . . . . 168 .
3.3.3.1 Degree of Alkylation and Substitution of C Atoms . . . . . . . . 168 .
3.3.3.2 Molecular Size and Relaxation Mechanisms . . . . . . . . . . . 168 .
3.3.3.3 Anisotropy of Molecular Motion . . . . . . . . . . . . . . . . 169 .
3.3.3.4 Internal Molecular Motion . . . . . . . . . . . . . . . . . . . . 172
3.3.3.5 Association and Solvation of Molecules and Ions . . . . . . . . . . 178
3.3.3.6 Determination of Quadrupole Relaxation Times and
Coupling Constants from 13C Spin-Lattice Relaxation Times . . . . . 180
3.3.4 Medium and Temperature Effects . . . . . . . . . . . . . . . . . 181

4 I3C N M R Spectroscopy of Organic Compounds . . . . 183

4.1 Saturated Hydrocarbons . . . . . . . . . . . . . . . . . . . . . 183
4.1.1 Alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
4.1.2 Cycloalkanes . . . . . . . . . . . . . . . . . . . . . . . . . . 186
4.1.3 Polycycloalkanes . . . . . . . . . . . . . . . . . . . . . . . . 189
4.2 Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
4.2.1 Open-Chain Alkenes and Dienes . . . . . . . . . . . . . . . . . 192
4.2.2 Cycloalkenes . . . . . . . . . . . . . . . . . . . . . . . . . . 194
4.3 Alkynes and Allenes . . . . . . . . . . . . . . . . . . . . . . . 196
4.4 Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
4.4.1 Alkyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . 198
4.4.2 Cycloalkyl Halides . . . . . . . . . . . . . . . . . . . . . . . 203
4.4.3 Alkenyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . 205
4.4.4 Carbon-Fluorine Coupling Constants in Alkyl and Cyloalkyl
Fluorides . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
4.5 Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
4.5.1 Alkanols . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
4.5.2 Cycloalkanols . . . . . . . . . . . . . . . . . . . . . . . . . 209
4.6 Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
4.6.1 Dialkyl Ethers . . . . . . . . . . . . . . . . . . . . . . . . . 213
4.6.2 Enol Ethers and Alkynyl Ethers . . . . . . . . . . . . . . . . . . 215
4.7 Carbonyl Compounds . . . . . . . . . . . . . . . . . . . . . . 215
4.7.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
4.7.2 Aldehydes and Ketones . . . . . . . . . . . . . . . . . . . . . 216
4.7.3 Quinones and Annulenones . . . . . . . . . . . . . . . . . . . . 222
4.7.4 Carboxylic Acids and Derivatives . . . . . . . . . . . . . . . . . 226
XIV Contents

4.8 Aliphatic Organosulfur Compounds . . . . . . . . . . . . . . . . 233

4.9 Aliphatic Organonitrogen Compounds . . . . . . . . . . . . . . . 236
4.9.1 Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
4.9.2 Enamines. Enaminoaldehydes. Cyanines . . . . . . . . . . . . . . 238
4.9.3 Imines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
4.9.4 Nitriles and Isonitriles . . . . . . . . . . . . . . . . . . . . . . 242
4.9.5 Azacumulenes . . . . . . . . . . . . . . . . . . . . . . . . . 244
4.9.6 Nitroso and Nitro Compounds . . . . . . . . . . . . . . . . . . 246
4.10 Organophosphorus Compounds . . . . . . . . . . . . . . . . . . 247
4.10.1 Survey of Carbon-13 Shifts . . . . . . . . . . . . . . . . . . . . 247
4.10.2 Carbon-Phosphorus Couplings . . . . . . . . . . . . . . . . . . 250
4.11 Aromatic Compounds . . . . . . . . . . . . . . . . . . .
254 . . .
4.11.1 General . . . . . . . . . . . . . . . . . . . . . . . . .
254 . . .
4.11.2 Substituted Benzenes . . . . . . . . . . . . . . . . . . .
255 . . .
4.11.3 Substituted Naphthalenes . . . . . . . . . . . . . . . . .
263 . . .
4.11.4 Benzocycloalkenes and Hydroaromatic Compounds . . . . . . . . . 264
4.11.5 Fused and Bridged Aromatic Rings . . . . . . . . . . . . . . . . 265
4.11.6 Typical Coupling Constants . . . . . . . . . . . . . . . . . . . 266
4.1 1.7 3C- and 12C-Enriched Aromatic Compounds for
Structural Assignments and Mechanistic Studies . . . . . . . . . . . 270
4.12 Heterocyclic Compounds . . . . . . . . . . . . . . . . . . . . . 272
4.12.1 Heterocycloalkanes . . . . . . . . . . . . . . . . . . . . . . . 272
4.12.2 Non-Aromatic Heterocycles with sp2 Ring Carbons . . . . . . . . . 276
4.12.3 Heteroaromatic Compounds . . . . . . . . . . . . . . . . . . . 281
4.12.4 Typical Coupling Constants . . . . . . . . . . . . . . . . . . . 286
4.13 Organometallic Compounds . . . . . . . . . . . . . . . . . . . 293
4.13.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
4.13.2 Group I Organometallic Compounds . . . . . . . . . . . . . . . 295
4.13.3 Group I1 Organometallic Compounds . . . . . . . . . . . . . . . 295
4.13.4 Group I11 Organometallic Compounds . . . . . . . . . . . . . . . 296
4.13.5 Group IV Organometallic Compounds . . . . . . . . . . . . . . . 297
4.13.6 Organo-Transition-Metal Compounds . . . . . . . . . . . . . . . 300
4.14 Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
4.14.1 Carbocations . . . . . . . . . . . . . . . . . . . . . . . . . . 302
4.14.2 Carbanions . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
4.15 Synthetic Polymers . . . . . . . . . . . . . . . . . . . . . . . 308
4.15.1 Tacticity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
4.15.2 Configurational Isomerism . . . . . . . . . . . . . . . . . . . . 311
4.15.3 Segmental Mobility . . . . . . . . . . . . . . . . . . . . . . . 313
4.16 Substituent Increments: Summary and Application . . . . . . . . . 313
4.16.1 Substituted Alkanes . . . . . . . . . . . . . . . . . . . . . . . 314
4.16.2 Substituted Cyclohexanes and Bicyclo[2.2.2]heptanes. . . . . . . . . 316
 Contents XV

4.16.3 Substituted Alkenes . . . . . . . . . . . . . . . . . . . . . . . 318

4.16.4 Substituted Benzenes . . . . . . . . . . . . . . . . . . . . . .
319
4.16.5 Substituted Pyridines . . . . . . . . . . . . . . . . . . . . . . . 322
4.16.6 Nitrogen Increments in Fused Heterocycles . . . . . . . . . . . . . 322

5 13CN M R Spectra of Natural Products . . . . . . . . . 327

5.1 Terpenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
5.2 Steroids . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
5.2.1 Androstanes. Pregnanes and Estranes . . . . . . . . . . . . . . . 338
5.2.2 Cholestanes and Cholanes . . . . . . . . . . . . . . . . . . . . 340
5.2.3 Cardenolides and Sapogenins . . . . . . . . . . . . . . . . . . . 358
5.3 Alkaloids . . . . . . . . . . . . . . . . . . . . . . . . . . . 360
5.4 Carbohydrates . . . . . . . . . . . . . . . . . . . . . . . . . 379
5.4.1 Monomeric Aldoses and Ketoses . . . . . . . . . . . . . . . . . 380
5.4.2 Di- and Polysaccharides . . . . . . . . . . . . . . . . . . . . . 394
5.4.3 Polyols . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
5.4.4 Aldonic Acids . . . . . . . . . . . . . . . . . . . . . . . . . 397
5.4.5 Inositols . . . . . . . . . . . . . . . . . . . . . . . . . . . . 400
5.5 Nucleosides and Nucleotides . . . . . . . . . . . . . . . . . . . 401
5.5.1 Assignment of the Purine Resonances . . . . . . . . . . . . . . . 402
5.5.2 Assignment of the Pyrimidine Resonances . . . . . . . . . . . . . 409
5.5.3 Assignment of the Isoalloxazine Resonances . . . . . . . . . . . . 409
5.5.4 Assignment of the Sugar and Polyol Carbon Atoms . . . . . . . . . 409
5.5.5 Correlations of 13C Chemical Shifts with
Other Physicochemical Parameters . . . . . . . . . . . . . . . . . 410
5.5.6 Nucleic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . 412
5.6 Amino Acids . . . . . . . . . . . . . . . . . . . . . . . . . . 414
5.6.1 13C Chemical Shifts of Amino Acids . . . . . . . . . . . . . . . . 414
5.6.2 pH-Dependence of the I3C Chemical Shift Values of Amino Acids . . . 420
5.6.3 Prediction of Carbon Shifts and their Correlation with
Other Physicochemical Parameters . . . . . . . . . . . . . . . . . 421
5.7 Peptides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
5.7.1 Oligopeptides . . . . . . . . . . . . . . . . . . . . . . . . . . 422
5.7.2 Homopolymeric Polypeptides . . . . . . . . . . . . . . . . . . . 436
5.7.3 Proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
5.8 Porphyrins . . . . . . . . . . . . . . . . . . . . . . . . . . . 441
5.9 Coumarins . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.10 Flavonoids . . . . . . . . . . . . . . . . . . . . . . . . . . . 450
5.1 1 Elucidation of Biosynthetic Pathways . . . . . . . . . . . . . . . 457
5.11.1 Radicinin . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
XVI Contents

5.11.2 Asperlin . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457

5.11.3 Cycloheximide . . . . . . . . . . . . . . . . . . . . . . . . . 457
5.11.4 Averufin. Versicolorin A and their Relation to Aflatoxin B. . . . . . . 459
5.11.5 Virescenosides . . . . . . . . . . . . . . . . . . . . . . . . . 459
5.11.6 Methyl Palmitoleate . . . . . . . . . . . . . . . . . . . . . . . 459
5.11.7 Sepedonin . . . . . . . . . . . . . . . . . . . . . . . . . . . 462
5.11.8 Antibiotic X-537 A . . . . . . . . . . . . . . . . . . . . . . . 463
5.11.9 Cephalosporin . . . . . . . . . . . . . . . . . . . . . . . . . 463
5.11.10 Prodigiosin . . . . . . . . . . . . . . . . . . . . . . . . . . . 465
5.11.11 Myxovirescin A. . . . . . . . . . . . . . . . . . . . . . . . . 465
5.12 Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . 467

6 References . . . . . . . . . . . . . . . . . . . . . . . . . 469

Subject Index . . . . . . . . . . 499

34 2 Instrumental Methods of I3C NMR Spectroscopy

uncorrected
(a)

'6 D6

corrected

-
1 : : I I : : : : : I I : : : : : I : ; :
200 150 100 50 0

6, P P ~
Fig. 2.13. (a, c) 22.63 MHz PFT 13C{1H} NMR spectrum of methyl acetate (20%) in hexa-
deuteriobenzene (75%) and tetramethylsilane (5%); 256 accumulated pulse interferograms;
(a) real part before phase correction;
(b) phase correction according to eq. (2.15), achieved by using the phase shifts indicated above;
+
extrapolation of the linear plot cp ( v ) yields qA= 15" and cpe = + 280"; for correction, the signs
have to be changed, thus qA= - 15" and cpB = - 280";
(c) real part after phase correction according to (b).
 Subjec t index
This index emphasizes chemical classes in italic type. Page numbers refer to carbon shifts if not
otherwise specified. Individual compounds are included if their spectra are reproduced or if they are
important parent skeletons.

Absorption-mode spectra 13f. one-bond 136f.

- -

example 16, 35
- ~three-bond 144
-

Absorption signal 5 - - two-bond 141, 143

Accumulation - shifts

- of spectra 21 - - aliphatic 114, 217 (table)

- of FID signals 41 - - aromatic 221 (table), 260 (table)
Acetals 220 - substituent increments 220
Acetates 228 (table) Aldofuranoses 383 f. (table)
Acetic amide, N,N-dimethyltrichloro- Aldohexoses 380, 381 f. (table)
- temp. dep. spectra 130 Aldonic acids 400 (table)
Acet oacetate, ethyl- Aldonolactones 400 (table)
- spectrum 232 Aldopentoses 380 f. (table)
Acetone Aldopyranoses 381 f. (table)
- spectrum 16 Alkaliorganic compounds 295
Acetophenones 221 f. (table) Alkaloids 360 ff. (table)
Acet y lacetone - aconitines 374
- spectra 52 - amarylidaceae 370
Acetylation shift - aporphines 369
- of alcohols 207, 230 - bisindoles 367
- of steroids 337, 340 - bisisoquinolines 371
Acetylenes 196 - colchicines 373
- see Alkynes - dihydroindoles 363
Acids - diterpenes 373f.
- see carboxylic and sulfonic acids - ergolines 366f.
Aconitine alkaloids 374 - indoles 363f.
Acquisition time 30 - isoquinolines 368 ff.
Actinomycin D - izidines 361 ff.
- 2D CH shift correlations 426f. - lysergic acid derivatives 366f.
Acyl cations 304 - morphines 370
Adamantane - peptides 377f.
~ spin-lattice relaxation times 61 (fig.) - piperidines 360f.
Additivity relationships - proaporphines 369
- alkanes 184f. - pyridines 360f.
Aflatoxin B, - pyrrolidines 360 f.
- biosynthesis 459 - pyrrolizidines 361
- 2D CH shift correlation 446 - quinines 372
Alcohols 206 ff. - quinolines 371
- see alkanols and cycloalkanols - quinolizidines 362 f.
- spin-lattice relaxation times 179 - steroids 375
A ldehydes- ~ tetrahydro-p-carbolins 364 f.
- CH couplings- - tropanes 361
 500 Subject index

Alkaloids Alkynyl halides 199 (table)

- with exocyclic nitrogen 373 Allenes 198 (table)
- yuzurimines 373 Ally1 ions 302, 306
Alkanals 216 ff. Alternately pulsed 13C{1H}NMR 50
- see aldehydes A m ides
Alkane derivatives - CN couplings 156
- shifts - shifts 229 (table)
- - substituent increments 315 (table) Amide resonance 231
Alkanes Amidines 241
- CC couplings 149 Amines
- CH couplings - CN couplings 156
- - one-bond 135f. - pH (protonation) shifts 121, 236
- - three-bond 143 - shift increments 236, 238 (table)
- - two-bond 141 - shifts

- shifts 111, 183 (table) - - aliphatic 237 (table)

- - additivity relationship 184f. - - aromatic 257 (table)
- - increment system 184 - - heterocyclic 273f. (tables)
- - steric effect 185f. Amino acids
A lkano1s - CN couplings 159
- acetylation shifts 207, 230 - pH shifts 121, 420f.
- protonation shifts 207 - protecting groups 414
- shift increments 207 - shifts 415ff. (table)
- shifts 208 (table) - - pH dependence 420
Alkene-n-complexes 300 f. Ammonium salts 228, 237, 260
Alkenes Androstanes
- CC couplings 150, 154, (EIZ) - CC couplings 338
- CH couplings - shifts 341 (table)
- - one-bond 135ff. 5 P-Androstan-3,17-dione
- - three-bond 144 - 2D CH correlation 95
- - two-bond 141 An ilines
- shifts 111, 116, 192f. (table) - CN couplings 156, 158
- - influence of configuration 192f. - shifts 113, 257 (table)
- - substituent increments 194, 318 (table) Angular momentum 1
Alkenyl halides Anhydrides 229 (table)
- CH couplings 199 (table) Anh ydropanaxadiol
- shifts 199 (table) - spectra 84
Alkylation Anisotropic rotation, effect on T , 169f.
- effect on spin-lattice relaxation 168 Annulenes
- shift of alcohols 213 - bridged 266
Alkyl halides Annulenones 224 f.
- CF couplings 162 (table) Anthracenes 265 f.
- CH couplings Antibiotics 457 f., 463, 468
- - one-bond 136 Aporphine alkaloids 369
- shifts 111, 199 (table) APT (attached proton test) 75, 78
- solvent shifts 201 (table) Aromatic compounds 254 ff.
Alkynes - CC couplings 268
- CC couplings 150 - C F couplings 269
- CH couplings - CH couplings 145f., 266
- - one-bond 135f. - shifts 256ff. (table), 260f. (table),
- - three-bond 144 263 (table)
- - two-bond 141 - - substituent increments 264, 319f. (table)
- shift increments 197 Arrhenius equation 130, 181
- shifts 111, 197 (table) Axiallequatorial configuration
Alkynols 208 - coupling differences 205
Alkynylethers 21 5 - shift differences 115, 203, 209ff. (table),
- shifts 214 (table) 212, 316 (table), 379, 393
 Subject index 501

Azacumulenes 244 f. Biotin

Azacy cloalkanes - J-resolved 2D spectra 90f.
- CH couplings 288 Biphenyl, 4,4'-dimethyl-
- shifts 273 (table) - temp. dep. spin-lattice relaxation 182 (fig.)
Azadecalins 276 Bipheny Is
Azapolycycles 277 - shifts 256
Azines - spin-lattice relaxation times 174, 182
- CH couplings 289 Bipyridine, 2,2'-
- shifts 283 (table) - inversion-recovery spectra 292
Aziridines (Aziranes) Bipyrrole, 2,2'-
- CH couplings 138, 288 - spectra 291
- shifts 273 Bisindole alkaloids 367
Azo compounds 257 Bisisoquinoline alkaloids 371
Azoles Bloch equations 8 ff.
- CH couplings 139, 146, 288 Boltzmann distribution of spins 5, 7, 22, 78
- shifts 282 (table) Boron compounds
Azoxy compounds - see organoboron compounds
- CN couplings 156 Bulk susceptibilities 17
Butadiene, 1,3-, 3-(isopinocampheoxy)-
Benzaldehy des 2-methyl-
- CH couplings 143, 146, 267 - DEPT, 2D INADEQUATE 105
- shifts 221 (table), 260 - 2D CH correlation cover page
Benzene derivatives Butadienes
- CC couplings 150f. (table), 268 (table) - see dienes
- - one-bond 150
- - three-bond 154 Calibration of NMR spectra 16
- - two-bond 151 D-Camphor
- C F couplings 269 (table) - J-modulated spectra 77
- CH couplings 139, 145 (table), 266 - isotropic shifts 125 (fig.)
- - one-bond 139, 145 Camphor derivatives
- - three-bond 145f. - CH couplings 329 (table)
~ - two-bond 142, 145 - shifts 331 (table)
- shift prediction (examples) 321 Carbanions 112
- shifts 113, 256ff. (tables) - CN couplings 308
- - alkyl-, alkenyl-, alkynyl- 256 - shifts 112, 305f. (table)
- - disubstituted 260f. Carbenium ions
~ - fused 265f. - CH couplings, averaging 304
- - mixed disubstituted 256f. - shifts 113, 303 (table)
- - polyalkyl- 260 Carbocations 113, 303 f.
- - polysubstituted 261 Carbodiimides 245
- - substituent increments 319f. (table) P-Carbolin alkaloids 364 f.
- spin-lattice relaxation times 170 Carbohydrates 379 ff.
(table) - aldonic acids 400 (table)
Benzenonium ions 305 - aldonolactones 400 (table)
Benzocy cloalkenes - disaccharides 393f. (table)
- CH couplings 265 (table) - glycosides 383f. (table)
- shifts 265 (table) - inositols 401 (table)
Benzoic acid esters 231 (table) - monosaccharides 380, 381 ff. (table)
Benzoic acids 257, 260f. - - CC couplings 148
Benzyl derivatives 256 - - CH couplings 27, 142
Benzyl ions 303, 307 - polyols 398 (table)
Bicycloalkanones 219 - polysaccharides 393
Bicyclo[2,2,l]heptanes Carbon chemical shifts 107ff.
- see norbornanes - comparison with proton shifts 108, 118
Biopolymers 393, 423 - conversion 108
Biosynthetic pathways 451 ff. - correlation with UV absorption 110
 502 Subject index

Carbon chemical shifts - longer-range 152ff.

-
- influence of - measurement by INADEQUATE 84f.,
-
- - anisotropic fields 116, 255 350
- - carbon hybridization 111 - - one-bond 147ff.
- - charge density 111, 254, 281, 265, - - three-bond 153ff.
411 (fig.), 422 (fig.) - - _ comparison with CH and
- - configuration 115 f., 203,209 ff., 229,272, H H couplings 153
274 - - two-bond 152
- - conformation 116, 131, 274ff., 394 - carbon-deuterium 109 (table), 147
- - conjugation 114 - carbon-fluorine 161 f.
- - crowded substituents 112 - - longer-range 162 (table), 206 (table),
- - diastereotopic effects 205 269 (table), 340 (table)
- - dilution 120 - - - through-space mechanism 270
- - electric fields 116, 121 - - one-bond 162 (table), 206 (table),
- - electron deficiency 113 269 (table), 340 (table)
- - electron density 111, 254, 281, 395 (fig.) - carbon-germanium 293, 298
- - electron donation 113,205,215,222,258, - carbon-lead 293, 299 (table)
28 1 - carbon-lithium 293, 295
- - electronegativity 111 f., 41 1 (fig.) - carbon-mercury 161, 293, 301
- - electronic excitation energy 110, 233 - carbon-metal
- - electron releasing 113, 205, 215, 222, 258, - - prediction 294
28 1 - carbon-nitrogen 155ff.
- - electron withdrawing 113f., 216, 224, - - as assignment aid 158
258, 281 - - longer-range 157f.
- - heavy atoms 117, 233, 300 - - lone pair influences 156ff.
- - homoconjugation 194, 219 - - one-bond 155f., 159 (table)
- - hybridization 111 - carbon-phosphorus 161, 250ff.
- - hydrogen bonding 117 f., 222 - - longer range 251 (table), 410
- - n-inductive effect 255 - - - structural influences 252 f. (table)
- - intramolecular fields 116, 121 - - one-bond 251 (table)
- - isotopic substitution 117, 379 - carbon-platinum 293
- - N-oxidation 286 - carbon-proton 134ff., 266
- - pH (protonation) 121 f., 236, 286, 420f. - - influence of
- - resonance (mesomeric effects) 113, 255, - - - bond angle 141
281 - - - carbon hybridization 134 f., 135 (fig.)
- _ ring current 117 - - - carbon s character 135 (fig.)
- - solvents 118, 120, 201 - - _ chelated hydrogen 147
- - steric interactions ( y effects) 115f., 203, - - _ configuration 138, 142 ff., 266
213, 218, 220f., 255, 259, 307 - - - distance 146
- - temperature 131ff. - - - electronegativity 134f., 139, 142, 146
- - unshared electron pairs 112, 244 - - - hydrogen bonding 118
- prediction 314ff. - - _ ring strain 138
- references 17, 108 - - - solvent 118 (table), 140
- survey IlOff., 119 - - - substituent crowding 135, 136 (table),
Carbon coupling constants 133ff. 138
- calculation 134 - - longer-range 134ff.
- carbon-aluminum 293 - - - comparison with HH couplings
- carbon-boron 161, 293, 297 140 (table)
- carbon-cadmium 161, 293 - - three-bond 143ff. (table)
- carbon-carbon 147 ff., 268 - - two-bond 141f. (table)
- - influence of - - one-bond 134ff. (tables)
- - - bond angle 141 - carbon-selenium 161
- - _ bond order 153 - carbon-silicon 161, 293, 299 (table)
- - - carbon hybridization 150f. - carbon-tellurium 161
- - _ configuration 152 ff. - carbon-thallium 161, 293, 297 (table)
- _ - electronegativity 152 - carbon-tin 161, 298f. (tables)
 Subject index 503

- carbon-tungsten 293 CAT method 21

Carbon-13(12) labelling 270f., 457ff. CCCOSY 148
Carbon s character Cephalosporins
- influence on - biosynthesis 463
- - CC couplings 151 (fig.) - shifts 464 (table), 468
- - CH couplings 135 (fig.) Chalcones 452
- - CP couplings 252 .rc-Charge density
Carbon-13 satellites 18, 79, 85 - vs. 13C shift 111 (fig.), 254, 281
Carbon tetrachloride Chemical shift(s) 15f., 107ff.
- spin-lattice relaxation time 57 (fig.) - see carbon-13 chemical shifts

- spin-spin relaxation time 65 (fig.) Chemical shift anisotropy relaxation 163

Carbonyl compounds 215 ff. Chemical shift ranges 119 (fig.)
- aldehydes 216ff., 221, 260 Chiral shift reagents 124
- carboxylic acids and derivatives 226 ff., 256, Chloroacetylation shifts
260 - of alcohols 230
- CH couplings Chloroform
- - one-bond 137f. - solvent shifts 118 (table), 120
- - three-bond 144 - SPT spectra 79
- - two-bond 141, 143 Chlorophyll derivatives
- ketones 216ff. - coordination shifts 441
- phenones 116, 221 f. (table) - shifts 443f. (table)
- quinones 222ff. Cholanes 340, 357 (table)
- shifts Cholestanes 340
- - correlation with UV absorption 110, 219 - CC couplings 350
- - in comparison with thiocarbonyl - shifts 351 f. (table)
compounds 233 Cholestan-3-one, 5a-
Carbonyls - spectra 349
- see metal carbonyls Chromones 279
Carboxylic acids cis-trans isomerism of
- CC couplings - alkenes 116, 192f. (table)
- - one-bond 149, 152 - cycloalkanes 115, 187 (table)
- - three-bond 153f. - cycloalkanols 210 (table)
- - two-bond 152 - nitrosamines 246
- CH couplings - oximes 137, 241
- - one-bond 137f. - polymers 311 f.
- - two-bound 141 Coalescence temperature 129
- pH shifts 121 Colchicine alkaloids 373
- shift increments 227, 230 Colchicine
- shifts 225f. (table) - spectra 45
- - aliphatic 225f. (table) COLOC 96
- - aromatic 257, 260f. (table) Complexation shifts
- - influence of hydrogen bonding 227 - boric acid 410
- solvent shifts 230 - titanium tetrachloride 445
- a,P-unsaturated Computer simulation of lineshapes 130 (fig.)
- - substituent increments 230 Configuration
- - shifts 228 (table) - influence on

Curboxylic acid derivatives - - C F couplings 205f.

- shifts 228f. (table) - - CH couplings 137
- amides 229 (table), 231 - - CP couplings 252
- anhydrides 229 (table), 231 - - shifts 115f., 187, 192, 210, 203f., 209ff.,
- esters 228 (table), 231 215, 225f., 229, 241, 246, 274
- halides 229 (table), 232 Conformation
Curdenolides 359 (table) - from spin-lattice relaxation times 172
Carotenoids 335 (table) - from temp. dep. spectra 131f., 186, 276
Carr-Purcell-Meiboom-Gill spin echo Conjugation
(CPMGSE) experiments 63 f. - influence on shifts 114
 504 Subject index

Continuous wave (CW) NMR 22 - shifts 204 (tables)

- sensitivity relative to PFT 41 Cycloalkynes 197f.
Contour plot 88 Cyclodienes 195 (table)
Conversion of I3C shifts 108 Cyclohexane, cis-l,2-dimethyl-
Cope systems - temp. dep. spectra 132
- shifts 195 (table) Cyclohexanes
- - temp. dependence 196 - C F couplings 206 (table)
Correlation - CH couplings 139, 186
- see shift correlation - shifts 187 (table), 210 (table), 236
Correlation function 167 (fig.) - - substituent increments 188,
Correlation time, effective 166 316 (table)
- VS. TI, T2 167 (fig.) Cyclohexanol, cis- and trans-4-t-butyl-
COSY 96f. - spectrum 209
- with delay 98 Cyclohexanols
Coumarins - shift increments 212
- CH couplings 288, 445 - shifts 210 (table)
- shifts 278, 445, 448ff. (table) Cyclononane
Coumestanes 468 - temp. dep. spectra 131
Coupling constants 18 f., 133 Cyclopen tanes
- see carbon-1 3 coupling constants - shift increments 188
- signs 19, 80 - shifts 187 (table)
Coupling, residual 50 Cyclophanes 265
Cumulenes 198 (table) Cyclopolyene-n-complexes 294 (table)
Cyanides 243 Cyclopolyenes
- see nitriles - shifts 195 (table)
Cyanines - - homoconjugative effect 194
- CH couplings 240 Cyclopolyenones
- shifts 239 - see annulenones
Cycloalkanes Cyclopolyenyl anions 306
- CC couplings 149, 151 (table), 153, Cyclopropanes
154 - CC couplings 149
- - one-bond 149 - CH couplings 138f., 154
- - three-bond 153f. - shifts 187
- - two-bond 151
- C F couplings 162 (table), 206 Decalins
- CH couplings 139 (table) - shift increments 191
- - one-bond 139 (table), 186 (table) - shifts 190, 209, 211 (table)
- - two-bond 140f. Decoupler pulse 81
- shifts 115 (cisjtrans), 186f., (tables) - calibration 82
- shift increments 188 Decoupling (spin decoupling) 43 ff.
Cycloalkanols - basic concept 43f.
- configurational isomerism 209 (fig.), - broadband 45
210 (table) - channel 71
- shift increments 212 (table) - gated 50
- shifts 210f. (table) - - for J-resolved 2D NMR 90
Cycloalkanones - inverse gated 50
- shifts 218 (table) - low-power noise 45
- - correlation with UV absorption 219 - noise 45
Cycloalkenes - off-resonance 47 ff.
- CH couplings 139 - pulsed 50f.
- shifts 117, 195 (table) - selective 53f., 94
Cycloalkenones 219 (table) DEFT 39f.
Cycloalkenyl cations 302 DEPT 80f.
Cycloalkyl halides Degree of alkylation
- C F couplings 206 (table) - influence on

- shift increments 203 - - shifts 112

 Subject index 505

- - spin-lattice relaxation times 168 Diterpene alkaloids 373 (table)

Degree of Substitution Diterpenes
- influence on - biosynthesis 459, 461
- - CH coupling constants 135f. - shifts 332 (table), 461 (table)
- - shift 112 Dithianes, 1,3-
- - spin-lattice relaxation time 168 - shifts 233, 275 (table)
Deshielding 17 Dodecahedrane 189
Detection period 75, 87 Double quantum frequency 102
Deuterated solvents Double quantum transfer 86, 102
- shifts and couplings 109 (table) Double resonance techniques in
Deuterium isotopic effects 117, 379 I3C NMR 43ff.
Deuterium labeling 337, 379 Dwell time 30
Diamines
- aliphatic 237 Ecgonine
- aromatic 260 - 2D shift correlations 98 (fig.)
Diamagnetic shielding term 110 Editing of spectra 82f.
Diastereotopic shifts Electron deficiency
- of alcohols 206 - effect on shifts 113
Diazoalkanes Electronegativity
- CN couplings 156 - effect on

- shifts 114, 244 - - CH coupling 134f., 142, 144, 146

Dicarboxylic acid anhydrides 229 (table) - - CP coupling 252, 254
Dicarboxylic acids - - 13C shifts 111
- aliphatic 226 (table) Electron density vs. 13C shifts 111, 395 (fig.)
- aromatic 260 Electron withdrawing
o-Dichlorobenzene - effect on 13C shifts 113
- TI, T , 67 (fig.) Enamines 239, 280
Dienes Enaminoaldehydes 240
- shifts 114, 193 (table) Enantiomers
- - influence of - signal separation 124
- - _ configuration 194 Endolexo configuration
- - - donor substituents 239 - coupling differences 205f., 253, 301
Dienyl anions 306 (table) - shift differences 203f., 212, 236, 317 (table)
Digital filtering 36 Energy of activation 130
Digital resolution 36 f. Enole thers
Digitization 30 - aliphatic 214 (table)
Dihalobenzenes 260 - heterocyclic
Dihydroflavones 454 (table) - - CH couplings 289
Dilution shifts 120, 285 - - shifts 276, 278
Diones (diketones) Enones 114, 218 (table), 219
- keto-enol tautomerism 220 Enthalpy of activation 130
- shifts 218, 257 Equatorial/axial configuration
Dipeptides 423 (table), 427 (table) - shift difference 115, 203, 209ff. (table), 212,
Diphenylether 316 (table), 379, 393
- spin-lattice relaxation times 58 (fig.) Equilibrium magnetization 7, 22
Diphosphines 249 Ergoline alkaloids 366 f.
Dipolar relaxation 46, 164, 166f. Esterification shift
Dipole-dipole relaxation mechanism 46, 164, - of carboxylic acids 230
166f. - of steroids 337
Disaccharides 393, 396 (table) Esters 228 ff.
Dispersion spectrum 14 - see carboxylic acid derivatives

- example 35 Estranes 338, 341 f. (table)

Dissociation effects Ethane, 1,2-dimethoxy-
- on CN couplings 156ff. - spectra 49
- on shifts 121 f. Ethers
Disulfides 234 - aliphatic
506 Subject index

Ethers - CC couplings 154f.

- - shift increments 213 - C F couplings 270
- - shifts 214 (table) - CH couplings 266
- - steric influences 213 - shifts 266 (table)
- aromatic 257, 261, 263 Fused heterocycles
- heterocyclic - shifts 284 (table)
- - CH couplings 288 - - nitrogen increments 324
- - shifts 273, 277
Et hylbenzene D-Galactose
- spectrum 32 - spectrum 38
Evolution Gated decoupling 50
- period 75, 87 Gated spin-echo 75
- time 87 Gaussian multiplication 36
Exo/endo configuration Gibbs-Helmholtz equation 130
- see endo/exo configuration D-Glucose
Exponential multiplication 36 f. - I-l3C enriched
External lock 72 - - spectra 27
External reference 72, 108 - mutarotational equilibration

Eyring equation 128 - - spectra 380

- uniformly enriched

Fellgett principle 42 - - CCCOSY 148

Fermi contact mechanism G1ycylalanine
- of coupling 18f., 133f., 299 - isotropic shifts 126 (fig.)
Fermi contact shift 124 Glykolipids 497
Field-frequency lock 70 Glycosidation shifts 379, 385 f. (table), 452
Filtering of frequencies 31 Glycoside sequencing
Flavin adenine dinucleotide - by spin-lattice relaxation times 175
- spectra 402 Glycosides
Flavones (Flavonoids) - spin-lattice relaxation times 175
- CH couplings 288 - shifts 385f. (table), 450 (table)
- shifts 279, 452f. (table) Glycylalanine
Flavone glycosides 450 - isotropic shifts
Fluoroalkanes - _ spectra 126
- C F couplings 162, 206 Grignard reagents 258, 296 (table)
Folding back 31 - Schlenk equilibrium 295 f.
Formic acid, NOE 46 Guanidines 241 f.
Formyl compounds (aldehydes) Guanidinium ions 303
- CH couplings 137f., 141, 143f. Guttapercha
- shifts 114 - spectrum 312
Fourier series 29, 41 Gyromagnetic ratio 2
Fourier transform 29 - influence on line-broadening 308
Fourier transformation 33
Franganine Half-maximum intensity width 4
- 2D CH correlation 376 Halides
Free enthalpy of activation 130 - see alkyl halides, haloalkanes

Free induction decay (FID) 24f. - - and carboxylic acid halides

- examples 26f., 37 Hammet CJ constants vs. 13C shifts 259 (fig.)

- driven equilibrium FID 40 Haloalkanes
Fulvenes 195f. - C F couplings 162 (table)
Functional group shifts 118f. (fig.) - CH couplings

Fungal metabolites 457 f., 467 - - one-bond 136

Furanosides 383 f. (table) - - three-bond 144
Furans - shifts 111f., 199 (table)
- CH couplings 146 - solvent shifts 201 (table)
- shifts 282 Haloalkenes
Fused aromatic compounds - CH couplings 199 (table)
 Subject index 507

- shifts 199 (table) - of amides 229 (table), 231

Haloalkynes Homonuclear couplings 147ff.
- CH couplings 199 (table) Homoisoflavanones 456 (table)
- shifts 199 (table) Hormones
Halobenzenes - hypothalamic 430
- CF couplings 269 - peptides 430, 432 (table)
- CH couplings 145 - steroids 341 ff.
- shifts 256 - phyto- 467
Halome thanes Hybridization
- CH couplings 199 (table) - effects on

- shift prediction 200 - - 13C coupling constants 134f., 150f.,

- shifts 199 (table), 200 (fig.) 155f., 252
Halouracils 41 1 - - shifts 111
Heisenberg uncertainty relation 5 Hydrazones 240
Hemiacetals 232 Hydroaromatic compounds 265 (table)
Henderson-Hasselbach equation 122 Hydrocarbons 183ff.
Heterocycloalkanes - see alkanes, alkenes, alkynes, benzenes
- (Heteroalicyclic compounds) 272 ff. Hydrogen bonding, intramolecular
- CH couplings 139, 288 - effect on

- shifts 273 (table) - - shift 117

Heterocy cloalkenes - - CH coupling 147
- CH couplings 288f. (table) - - spin-lattice relaxation time 178f.
- shifts 278ff. (table) Hyperconjugation
Heteroaromatic compounds - influence on CH coupling 290
- CC couplings 150
- C F couplings 291 (table) Imaginary spectra 14, 36
- CH couplings 139, 142, 145f. Imidazoles
- - one-bond 139 (table), 145 - alkaloids 373
- - three-bond 145, 146 - CH couplings 288
- - two-bond 145, 146 - shifts 282
- CN couplings 156ff. Imines 240 ff.
- five-membered, benzo-fused 282 - aldimines 242 (table)
- five-membered, dibenzo-fused 283 - cyclic 280
- five-membered, monocyclic - oximes 241 (table)
- - CH couplings 288ff. (table) - ketimines 242 (table)
- - shifts 282 (table) Imonium salts 242
- fused heterocycles INADEQUATE
- - CH couplings 289f. . - one-dimensional 84 f.
- - shifts 284 (table) - two-dimensional 102f.
- six-membered, benzo-fused 283 - symmetrized 102, 105
- six-membered, dibenzo-fused 284 Increment systems 313 ff.
- six-membered, monocyclic - see shift and substituent increments

- - CF couplings 291 (table) Indoles 282

- - CH couplings 288ff. (table) - alkaloids 363ff.
- - shifts 284 (table) Indolizines 283
- shifts 282ff. (table) INEPT 80
- - nitrogen increments 324 Inositols 401 (table)
- - substituent increments 322f. Intermolecular interaction
Heteropolycycloalkanes 275, 277 (table) - effect on

Heteronuclear couplings 155ff., 160ff. - - spin-lattice relaxation time 176, 178f.

Heterospirocyclic compounds 277 (table) Internal reference 17, 72
Hexadeuteriodimethylsulfoxide Intramolecular mobility
- spectrum 26 - effect on

Hexamethylphosphoramide - - shifts 127ff.

- spectrum 37 - - spin-lattice relaxation time 166ff., 172f.
Hindered rotation 130, 172f. Inverse gated decoupling 50, 52
508 Subject index

Inversion of rings 131f. Lanthanoid shift reagents 124f.

Inversion recovery techniques 55 ff. Larmor equation 4, 15
Ionic species 302 ff. Larmor frequencies of nuclei 69 (fig.)
Isoalloxazines 402, 409 Larmor frequency 4
Isocyanates 245 Larmor precession 4
Isocyanides Lecithins
- see isonitriles - shifts 467
Isojlavones - spin-lattice relaxation times 176
- CH couplings 288 Line broadening
- shifts 279, 454 - due to fast relaxation 167
Isonitriles Line shape simulation 130 (fig.)
- CN couplings 159, 243 (table) Line width 4, 29
- shifts 243 (table) - temperature dependence 129 (fig.)
3-(Isopinocampheoxy)-2-methyl- 1,3-butadiene Lipids
- DEPT, 2D-INADEQUATE 105 - shifts 467
Isoquinolines - spin-lattice relaxation times 176
- alkaloids 368ff. Lithiumorganic compounds
- nitrogen increments 324 - see organolithium compounds
- shifts 283 Lock, lock signals 70
Isothiocyanates Longitudinal magnetization 7, 23
- CN couplings 159 Longitudinal relaxation time 8
- shifts 245 Long-range couplings
Isotope effect on I3C shifts 117 - CC 152ff.
Isotropic shifts 123ff. - C F 206, 270
Izidine alkaloids 361 f. - CH 140ff., 266f., 289f.
- CN 157ff.
J-modulation 75 f., 88 Lorentzian line shape 14
- for multiplicity determination 76 f. Low power noise decoupling 45
- in two-dimensional NMR 89 Lysergic acid alkaloids 366
J-modulated spin-echo (JMSE) 75 ff.
J-resolved 2D NMR 89f. Macrolides 468
Magic acid as NMR solvent 302
Karplus-Conroy relations 143, 153, 205, 253, Magnetic moment 2
395 Magnetic shielding constant 15, 110
Ketals 220 Magnetic susceptibility corrections 17
Ketenes 114 Magnetization
Ketenimines 244 - equilibrium 7, 22
Keto-enol tautomerism 52 (fig.), 220, - longitudinal 7, 23
232 (fig.) - partially relaxed 56f.
j-Ketoesters 232 - steady state 60
Ketones - transverse 12, 23
- shifts Magnetization vector 7, 23
- - aliphatic 217f. (table) Magnetogyric ratio (gyromagnetic ratio) 2
- - aromatic 221 f. (table), 257 Magnitude spectrum 14, 36
- - correlation with UV absorption 219 - example 35
- - homoconjugative effects 219 Magnets for NMR 69
- - steric effects 218 Measurement of 13C NMR parameters 21 ff.
Ketofuranoses 383 f. Mechanisms
Ketopyranoses 381 f. - of coupling 18f.
Ketoses 380 f. - of spin-lattice relaxation 163f.
Mechanistic studies 270 f.
Lactams 279 Medium shifts 12Of.
Lactones 278 Meisenheimer anions 307
D-Lactose Menthane derivatives 328 (table)
- 2D CH correlation 95 Menthol, (-)- 328
Lamb formula 110 - DEPT 83
 Subject index 509

- 2D-INADEQUATE 103 - two-dimensional 87 ff.

- spectra (NOE) 53 Mutarotation
Mercaptanes - example, spectra 380
- see thiols

Mercuryorganic compounds Naphtalene, 1,8-diiodo-

- see organomercury compounds - spectra 268
Mesomeric effects on shifts 113 Naphthalenes
Metal carbonyls 294, 300 - CC couplings 154ff.
Metallocenes 294 - C F couplings 270
Metalorganic compounds - CH couplings 266
- see organometal compounds - shifts 263 (table)
Methane derivatives - substituent increments 264
- CH couplings 136 Naphthyridines 284, 325
- shifts 112, 183, 200 (fig.) Natural rubber
Methanol - spectrum 312
- spectrum 33 Natural products 327 ff.
Methanol, tetradeuterio- Nickel, bis-(1,l -dimethylallyl)-isomers
- spectrum 37 - spectrum 301
6-Methoxy-1-tetralone Nicotine 361
- spectra 54 - spectra 54, 107
0-Methylation shifts Nitriles
- of carbohydrates 380 - CN couplings 159 (table)
Methyl carbon shieldings 185 - shifts 113, 243 (table), 31 1
Methylesterification Nitrites (esters) 246
- shifts 230 Nitroalkanes
Methylglycosides 383 f. (table) - CN couplings 156
Methyl rotation - shifts 247 (table)
- influence on spin-lattice relaxation 172 Nitroalkenes 247
Methyl substituent effects Nitrobenzenes 257, 261
- on cycloalkanes 188 Nitrosamines
- on decalins 190 - shifts 246 (table)
Modulation - - influence of

- see also J-modulation 75f., 88 _ _ _ configuration 246, 274

- of frequencies 45 - - _ conformation 274
- pulse interferograms 26 NMDR 43ff.
Molecular mobility NMR 4
- and spin-lattice relaxation 172ff. - detection 22, 24ff., 41
Molecular size - instrumentation 67ff.
- and spin-lattice relaxation 168 - in the rotating frame 1Of.
Monosaccharides 381 f. (table) - signals 29
- derivatives 383 (table) - spectrometer (schematic diagram)

Monoterpenes 327 ff. (tables) 68

Morphine alkaloids 370 - theory Iff.
Motional narrowing 167 - two-dimensional 87 ff.
Multiple resonance 43 ff. NOE 46f.
Mu1tiplet analysis - enhancement 46f., 50f.
- by DEPT 8Off. - measurement 51 f.
- - J-modulated spin-echo 75ff. - suppression 50f.
- - off-resonance decoupling 47 ff. Noise decoupling 45
Multiplet line intensities 20 Noise modulation 45
- after SPT 80 Nonbenzenoid aromatic ions
Multiplicity 17ff., 20 - shifts 111, 254, 302, 306
- analysis 75f., 80f., 82f. - - correlation with

- selection 82f. - - - n-charge density 111 (fig.)

Multipulse experiments Nonbonded (through-space) interactions
- one-dimensional 50 ff., 55 ff., 73 ff. - in carbon-fluorine coupling 161
 510 Subject index

Norbornanes group I 295

-

C F couplings 206 (table)

- group I1 295
-
- CHg couplings 301 - group I11 296
- CSn couplings 299 - group IV 297
- CT1 couplings 297 - methyl-metal compounds

- shifts 190 (table), 204 (tables), 211 (table), - - carbon-metal couplings 293 (table)
219, 236 - - shifts 293 (table)
- - substituent increments 317 (table) Organomercury compounds '

Norbornanols 21 1 (table) - couplings 301

Norbornanones 219, 331 (table) - shifts 293
Norbornenes 195, 219 Organonitrogen compounds 236 ff.
Norbornyl cation 305 Organophosphorus compounds
Nuclear induction 13, 24 - CP couplings 161, 251 (table), 413
Nuclear Overhauser effect (NOE) 46, 164f. - - influence of structural features

- NOE enhancement 46 f. 252 f. (table)

- measurement 51 f. - shifts 248 (table)
- quenching of 47 Organosilicon compounds
- relation to dipolar relaxation 164f. - CSi couplings 293, 299 (table)
Nuclear precession 2, 23 - shifts 293
Nuclear properties, Tab. 2 Organosulfur compounds
Nuclear shielding 15 - shift increments 233
Nuclear spin 1 - shifts 234 (table)
Nucleobases 404 ff. (table) Organothallium compounds
Nucleic acids 412 couplings 297
~

- homopolymeric Organotin compounds

- - CP couplings 413 (table) - couplings 299 (table)
- - helix random-coil tansition 412 - shifts 298 (table)
- - shifts 413 (table) Organotransition metal compounds 293 (table)
Nucleosides 401, 404 ff. (table) Orthoesters 220
Nucleotides 401, 404ff. (table) Overhauser effect
Nyquist equation 30 - see nuclear Overhauser effect

Oxacycloalkanes
Off-resonance decoupling 47 - CH couplings 288
~ frequency dependent 48 - shifts 273 (table)
Olefins 192ff. Oxacycloalkenes
- see alkenes - CH couplings 288
Oligopeptides 423 (table), 427 (table) - shifts 278 (table)
Oligosaccharides Oxapolycycles 277 (table)
- CH couplings 393 Oximes
- shifts 396 (table) - CN couplings 157
One-bond coupling 19, 134ff. - shifts 241 (table)
- CC 147ff. (table) - - influence of configuration 157, 160, 241
- CD 147 ~ spin-lattice relaxation times 173
- CF 162 (table), 206 Oxiranes
- CH 19, 134ff. (tables), 288f. (table) - CH couplings 138, 288
Organoboron compounds 297 - shifts 273
Organoelement compounds Oxonium salts 21 5
- group V 249 (table) Oxygen
Organolead compounds - influence on spin-lattice relaxation 165f.
- couplings 293, 299 (table)
- shifts 299 (table) Paramagnetic additives 47
Organolithium compounds Paramagnetic compounds
- CLi couplings 295 - as shift reagents 123ff.
- shifts 258, 278, 295 - influence on spin-lattice relaxation times 47
Organometallic compounds 293 ff. Paramagnetic relaxation 165f.
- carbon metal couplings 161, 293 f. Paramagnetic shielding term 110
 Subject index 511

Partially relaxed Fourier transform spectra 56 Polarization transfer 78, 92, 94

Penicillins 420 (table), 468 - non-selective (DEPT, INEPT) 80 f.
Peptides - selective (SPT) 79
- alkaloids 367, 377f. Polybutadiene
~ hormones 432f. (table) - partial spectra 312
- proline- 427f. (table) Poly cy cloalkanes
- shifts 423f. (table), 432f. (table) - shift increments 191
- spin-lattice relaxation times 431 - shifts 189, 190 (table)
Phase correction 33 ff. Polycycloalkenes 195 (table)
Phase cycling 86 Polycyclic (jiused) nitrogen heterocycles 284
Phase memory time 8 Polyenones 224
Phase of NMR signals 29 - see annulenones

Phase selection 30 Po ly isoprenes

pH (protonation) shifts 121f., 236, 286 - cis-trans-isomerism 177
Phenanthrenes 265 f. - spectra 312
Phenazine, 1-methoxycarbonyl- Polymers
- spectra 158 - cis-trans isomerism 178, 311f.
Phenazines - segmental mobility 177, 313
- CN couplings 158 - spin-lattice relaxation times 177f., 313
- shifts 284 - tacticity (stereosequence) 309 f.

Phenols 257, 260f. (table) Polyols 398 (table), 409

Phenones Polypeptides
- shifts 116, 221 f. (table) - helix random-coil transitions 436
- - influence of conformation 116, 259, 262 - shifts 423 f. (table), 427 f. (table),
Phosphabenzenes 432 f. (table)
- couplings 252, 254 - spin-lattice relaxation times 431, 437
- shifts 249 Polypropylene
Phosphates 248, 251 - spectra 310
Phosphetanes Polysaccharides 393
- CP couplings 252f. Population transfer 78 ff.
- spin-lattice relaxation times 174 - see polarization transfer
Phosphines (phosphanes) 248, 251 Porphyrins 442 (table)
Phosphinoxides 248, 251 Power spectra 14
Phosphites 248, 251 Pregnanes 338
Phosphonates 248, 251 - C F couplings 340 (table)
Phosphonium salts 248, 251 - shifts 341 (table)
Phosphonium ylides 248 f., 251 Preparation period 75
Phosphoramide, hexamethyl- Proaporphine alkaloids 369
- spectrum 37 Progressive saturation 60 ff.
Phosphorus compounds Propane 183
- CP coupling constants 160 (fig.), - three-bond coupling 143 (fig.)
250 ff. (tables) Propane, 1,I ,3,3-tetraethoxy-
- shifts 248f. (table) - spectra 49
Phthalic acid derivatives 231 f. Propynol
Phytohormones 467 - spin-lattice relaxation times 62 (fig.)
Piperidine (INADEQUATE) 86 Prostaglandins
Piperidines - shifts 467
- alkaloids 302 - spin-lattice relaxation times 179
- CC couplings 86 Proteins
- shifts 274 (table) - helix-random coil transitions 177
- - influence of - segmental mobility ( T I ) 177, 440

- - - configuration 272, 274 - shifts 438f. (table)

- - _ protonation 274 Protonation shifts 121f., 236, 286
Piperidinopentadienal Proton decoupling 43 ff.
- 2D shift correlation 101 - gated 50
pK Determination 122 - inverse gated 50f.
 512 Subject index

Proton decoupling - protonation shifts 286

~ low-power noise 45 ~ shifts 283, 286
- noise (broad-band) 44f. - - substituent increments 323 (table)
- off-resonance (single frequency off- Pyrimidine, 2,4,6-trichloro-
resonance) 47 ff. - spectra 51
- pulsed 50ff. Pyrimidines
- - for determination of NOE enhance- - CH couplings 145, 288ff.
ments 51f. - shifts 282, 404ff. (table), 409
- selective 53f., 94 Pyrones, 4-
Pseudo contact shift 124 - CH couplings 288
Pteridines 284 - shifts 278
Pulse angle 12, 22ff. Pyrroles
- adjustement 32 f. - CH couplings 146, 288ff.
Pulsed NMR 22ff. - CN couplings 157
Pulse Fourier Transform NMR 28ff. - shifts 282
Pulse frequency 31 Pyrrolidine alkaloids 361
Pulse interferograms 25 Pyrrolizidine alkaloids 361
- examples 26f., 37 Pyrylium salts 283
Pulse interval 30
Pulse sequences Quadrature detection (QD)
- Carr-Purcell-Meiboom-Gill 63 f. - digital quadrature detection) 32, 42
- COSY (Jeener) 97 Quadrupolar coupling constants
- DEFT 39f. - from spin-lattice relaxation times 180
- DEPT 8Of. Quadrupolar nuclei
- Inversion recovery 55f. - line-broadening 295
- INADEQUATE 85 Quantum number 1, 2
- Progressive saturation 60 f. Quinine alkaloids 372
- Saturation recovery 59f. Quinoline
- Spin-echo 73 - pH vs. shifts 122 (fig.)
- Two-dimensional 90, 93, 97 - pK determination 123 (fig.)
Pulse width 22ff. - solvent shifts 120 (fig.)
- adjustment 32, 33 (fig.) - spectra 42
Purines Quinolines
- C F couplings 291 - alkaloids 371
- CH couplings 290 - CH couplings 289
- shifts 284, 402, 404f. (table) - CN couplings 157f.
Pyranosides 385 ff. (table) - shifts 283
Pyrazole, 3-methyl-5-0x0-I-phenyl- - _ nitrogen increments 324
- spectra, tautomerism 287 Quinolizidine alkaloids 362 f.
Pyrazoles Quinones 223 (table)
- CH couplings 288
- shifts 282 Rate constants
Pyrenes - from shift difference 129 (fig.)
- CC couplings 155 Reaction mechanisms
- C F couplings 270 Real spectra 33f.
- shifts 266 Reeves effect 393
Pyr idines Referencing of I3C shifts 17, 108
- alkaloids 361 Relaxation 5 f.
- CC couplings 150 - in the rotating frame 12
- C F couplings 291 - see also spin-lattice and spin-spin relaxation

- CH couplings 145 Relaxation delay 39, 75

- - one-bond 139, 145, 288 Relaxation mechanisms 163ff.
- - three-bond 145, 290 Relaxation times 5 f.
- - two-bond 145, 289 - measurement 55 ff.
- CN couplings 156ff. RELAY 100
- dilution shifts 285 (fig.) Residual couplings 48 f.
 Subject index 513

Resolution enhancement 36 - alkanols 207

Resolution in PFT NMR 36f. - alkenes 194
Resonance effects on shifts 113 ~ alkynes 197
Restricted rotation 127 - amines 236
- influence on - benzenes 264, 319f. (table)
- - spin-lattice relaxation times 173 - carbonyl compounds 220
Rf field 4 - carboxylic acids 227, 230
Ribose, D- - cycloalkanes 188
- spectrum 394 - cycloalkanols 212
Rifamycins 468 - cycloalkyl halides 203
Ring inversion 127, 131 f. - cyclohexanes 316 (table)
Ring size - decalins 191
- influence on - naphthalenes 264
- - CH coupling 138f. - norbornanes 317 (table)
- - shift 118 - organosulfur compounds 233
Rotating frame of reference 9ff., 24 - pyridines 281, 323 f. (table)
Rotations - survey 313ff.
Shift reagents 124
Saccharose (Sucrose) Shift references in I3C NMR 17, 108
- spin-lattice relaxation time 182 (table) Shifts
Sample preparation 71 f. - see carbon chemical shifts

Sapogenins 359 (table) Signal enhancement

Satellite signals 18, 79 - by NOE 46f., 50f.
- due to - by polarization transfer 78ff.
- - carbon-carbon coupling 85 Signal intensity 4
- - carbon-metal coupling 298 - influence of

Saturation 6 - - spin-lattice relaxation time 39

Saturation-recovery method 59 f.
Scalar (coupling) relaxation 163
s-Character of carbon
- influence on coupling constants
151 (fig.)
- responding to polarization transfer 82
Signal to noise ratio 21
- see also sensitivity
135 (fig.), Siliconorganic compounds
- see organosilicon compounds

SEFT 75 Single frequency proton decoupling (off-

Segmental mobility resonance decoupling) 47 ff.
- effect on Solvents, deuterated
- - spin-lattice relaxation times 174f. - shifts and couplings 109 (table)
Selective proton decoupling 53 f. Solvent shifts 120 (fig.), 200, 201, 230
Sensitivity (signal :noise) - vs. dielectricity constant 200
- enhancement in 13C NMR Solvent effects
- - by polarization transfer 79ff. - on carbon-proton coupling 118
- - for protonated carbons 46 sp carbon
- - for slowly relaxing carbons 47 - coupling constants 135, 136, 138, 150f.
SFORD 47ff. - shifts 111, 119
Shielding constant 15, 110 sp2 carbon
Shielding of nuclei 15, 17, 110 - coupling constants 135, 137ff., 145,
Shift correlation, two-dimensional 150f.
- CC (INADEQUATE) 102ff. - shifts 111, 119
- CH (CH COSY) sp3 carbon
- - via one-bond coupling 92ff. - coupling constants 135, 136, 149, 150
- - via two- and three-bond coupling 96 - shifts 111, 119
- HH (COSY) 96ff. Spectral width 30
- relayed coherence transfer 100f. - to line width ratio 108
- survey 106 Spin 1
Shift increments 111, 313ff. Spin alignments 3
- alkane drivatives 315 (table) Spin-decoupling 43 ff.
- alkanes 184f. - see decoupling, double resonance
 514 Subject index

Spin-echo 63 f., 73 f. - alkaloids 375 (table)

- J-modulated 75 - androstanes 338, 341f. (table)
Spin-echo techniques 41, 63 f., 75 f. - cardenolides 359 (table)
Spin-lattice relaxation 5, 8 - cholanes 340, 357 (table)
- influence of molecular size 168 - cholestanes 340, 351f. (table)
- influence on signa1:noise 39, 50 - estranes 338, 348 (table)
- mechanisms 163ff. - pregnanes 441f. (table)
Spin-lattice relaxation time ( T I ) 6 - - fluorinated

- as assignment aid 168 - - - CF couplings 340 (table)

- correlation with - spin-lattice relaxation times 172
- - mobility and constitution 166ff. Structure elucidation
- - spin-spin relaxation time 167 - I3C NMR strategy 104ff.
- definition 8 Subspectra (DEPT) 82 f.
- influence of Substituent effects (increments) 118
- - anisotropic rotation 169f. - applications 313 ff.
- - association 178 - of alkoxy groups 213
- - configuration 173 - - alkyl groups 184f., 188, 194
- - conformation 171f. _ - amino groups 236
- - degree of alkylation 168 - - carbonyl groups 220
- - dissolved oxygen 166 - - carboxy groups 227
- - methyl rotation 172 - - halogens 111, 200, 203
- - molecular motion 166ff. - - hydroxy groups 207, 212
- - molecular size 168 - - sulfur containing groups 233
- - number of attached hydrogens 168 - on alkane carbons 111, 184, 233, 227,
- - paramagnetic compounds 165 315 (table)
- - segmental mobility 174f., 313 - - alkene carbons 193f., 227, 230,
- - solvent 181 318 (table)
- - steric interactions 173 - - alkyne carbons 197
_ - temperature 181 - - benzene carbons 258f., 264, 319f. (table)
_ - viscosity 181 - - cyclohexane carbons 188, 203, 212,
- influence on 316 (table)
- - signal intensity 39 - - decalin carbons 191, 212
- methods of measurement 55 ff. - - naphthalene carbons 264
- relation to - - norbornane carbons 203, 212, 317 (table)
- - spin-spin relaxation time 167 (fig.) - - pyridine carbons 281, 323f. (table)
Spin-locking FT experiments 66 f. - - steroid carbons 339
Spin population 3, 78 - survey 313 ff,
Spin-quantum number 1, 2 Sulfides (thioethers)
Spin-rotation relaxation 163f. - aliphatic 234
Spin-spin coupling 17 - aromatic 257
- mechanism 18f., 133f. Sulfinic acids 234
Spin-spin relaxation 6 Sulfones 234, 275
Spin-spin-relaxation time (T,) 6 Sulfonic acids and derivatives
- definition 8 - aliphatic 234

- influence on line-width 6 - aromatic 257

- measurement 63 ff. Sulfonium ions 234
- relation to Sulfoxide, hexadeuteriodimethyl-
- - spin-lattice relaxation time 167 (fig.) - spectrum 26
Spirocyclic compounds 277, 467 Sulfoxides 234, 275
SPT 79 Sugars
Stabilization of magnetic fields 70 - see carbohydrates
Stacked plots 88 Superconducting solenoids 70
Steric effects
- on shifts 115 Tacticity 202, 308 f.
- on spin-lattice relaxation 173 Taut omerism
Steroids 337 ff. - carbodiimides 245
 Subject index 515

- keto-enol 52, 220, 232 - shifts 281 f.

- pyrazolone (spectra) 287 Thioureas 235
- pyridinees 290 Titration curves 122
Temperature dependence Transition metal compounds
- of shifts 129 (fig.), 131 f., 300 - see organotransition metal compounds

Temperature effects on Transverse magnetization 12, 23

- spin-lattice relaxation times 181f. - components 28
Terpenes 327 ff. Transverse relaxation function 24
- bicyclic 328f. (table) Transverse relaxation time 12
- carotenoids 335 (table) 2,4,6-Trichloropyrimidine
- cyclic 328 (table) - spectra 51
- di- 332 (table) Tripeptides 423 (table)
- ionones 334 (table) Tropane alkaloids 361
- menthane derivatives 328 (table) Tropolone derivatives 224, 462
- mono- 328f. (tables) Two-dimensional NMR 87 ff.
- open-chain 327 (table) - basic concept 87
- retinals 334 (table) - columns 89
- spin-lattice relaxation times 172f., 179 - J-resolved 89
- tetra- 335 (table) - rows 88
Tetracyclins 468 - shift correlations

Tetradeuteriomethanol - - cc 102ff.
- spectrum 37 - - CH 92ff.
1,I ,3,3-Tetraethoxypropane - - HH 96ff.
- spectra 49 - - long-range CH 96
Tetrahedrane, tetra-t-butyl- 189 - - relayed coherence transfer 100
Tetrahydrocannabinol derivatives 467
Tetralone, 1-, 6-methoxy- U-mode 14
- spectrum 37 Uracils
Tetraterpenes 335 (table) - CH couplings 288
Thermodynamic data of interconversion 129f. - shifts 279, 404f. (table), 409, 411
Thiacycloalkanes Ureas
- CH couplings 288 - CN couplings 156
- shifts 273f. (tables) - shifts 279
Thiadecalins 276
Thiapolycycles 277 Vanilline
Thiazoles - spectra 267
- CH couplings 288 Variable temperature studies 130f.
- shifts 282 V-mode 14
Thiirans Vinyl halides
- CH couplings 138, 288 - CH couplings 199 (table)
- shifts 273 - shifts 199 (table)
Thioacetals 233 Virescenosides 459
Thioaldehydes 235 Viscosity effects on T I 181
Thiocarbonyl compounds 233, 235 (table) Vitamins 334, 351, 467
Thiocyanates 245
Thioethers Width of NMR lines
- aliphatic 234 - influence of
- aromatic 257 --T2 6
- heterocyclic 273 - - rate constants and temperature 128ff.
Thioketals 233 Woessner’s equations 169f.
Thioketones 233, 235 (table)
Thiols (mercaptans) Ylides 251, 253
- aliphatic 234 Y stabilization
- aromatic 257 - of carbanions 302
Thiophenes - of carbenium ions 308
- CH couplings 146, 288ff. Yuzurimine alkaloids 373