Structure Determination of Organic Compounds: Tables of Spectral Data

487 Pages·2020·9.192 MB·English

by  ERNO PRETSCH

NMR
MS
Ernö Pretsch
UV/Vis
Philippe Bühlmann
IR
Martin Badertscher
Structure
Determination
of Organic
Compounds
Tables of Spectral Data
Fifth Edition
Structure Determination of Organic Compounds
Ernö Pretsch • Philippe Bühlmann
Martin Badertscher
Structure Determination
of Organic Compounds
Tables of Spectral Data
Fifth Edition
Ernö Pretsch Philippe Bühlmann
Institute of Biogeochemistry Department of Chemistry
and Pollutant Dynamics University of Minnesota
ETH Zurich Minneapolis, MN, USA
Zürich, Switzerland
Martin Badertscher
Laboratory of Organic Chemistry
ETH Zurich
Zürich, Switzerland

Translation from the German language edition: Spektroskopische Daten zur Strukturaufklärung
organischer Verbindungen by Ernö Pretsch, Philippe Bühlmann, Martin Badertscher Copyright
© Springer-Verlag GmbH Deutschland, ein Teil von Springer Nature 1976, 1981, 1986, 2001,
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ISBN 978-3-662-62438-8 ISBN 978-3-662-62439-5 (eBook)
https://doi.org/10.1007/978-3-662-62439-5

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Preface
We present in this volume an updated collection of reference data and rules
for the interpretation of spectra obtained with the spectroscopic methods most
important to the structure elucidation of organic compounds: NMR spectroscopy
(1H, 13C, 15N, 19F, 29Si, and 31P), mass spectrometry (EI-MS and ESI-MS/MS),
and IR, Raman and UV/Vis spectroscopy. The basic idea is that a simultaneous
application of several of these techniques is much more powerful than even the
most sophisticated analysis of only one kind of spectrum. The ongoing success of
our combined approach corroborates its utility.
This new edition contains numerous new data added to existing tables and
figures. Additionally, we extended the scope of this volume taking into account new
developments in instrumentation.
We added novel collections of reference data for the interpretation of 15N and
29Si NMR spectra. The careful selection of relevant information from across the
literature seems to be unique in these fields.
An important recent development is the routine MS/MS analysis after soft
ionization (mainly ESI and MALDI). For this volume, we supplemented the existing
fragmentation rules for EI by rules for MS/MS analysis after soft ionization.
We thank Dr. Csaba Szántay und Áron Szigetvári (Spectroscopic Research
Department, Gedeon Richter AG, Budapest/Hungary) for critically reviewing the
new section on 15N NMR.
In spite of great efforts and many checks to eliminate errors, it is likely that some
mistakes and inconsistencies remain. We would like to encourage our readers to
contact us with comments and suggestions.
Zürich and Minneapolis, August 2020
V
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Scope and Organization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Abbreviations and Symbols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 Summary Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1 General Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.1 Calculation of the Number of Double Bond Equivalents from
the Molecular Formula . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.2 Properties of Selected Nuclei . . . . . . . . . . . . . . . . . . . . . . . 6
2.1.3 Volume Susceptibilities and Corrections for External
References in NMR Spectroscopy . . . . . . . . . . . . . . . . . . . 7
2.1.4 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.2 13C NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.3 1H NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.4 IR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.5 Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.5.1 Average Masses of Naturally Occurring Elements with Masses
and Representative Relative Abundances of Isotopes . . . . . . 20
2.5.2 Ranges of Natural Isotope Abundances of Selected Elements . . 27
2.5.3 Isotope Patterns of Naturally Occurring Elements . . . . . . . . 28
2.5.4 Calculation of Isotope Distributions. . . . . . . . . . . . . . . . . . 29
2.5.5 Isotopic Abundances of Various Combinations of Chlorine,
Bromine, Sulfur, and Silicon . . . . . . . . . . . . . . . . . . . . . . 31
2.5.6 Isotope Patterns of Combinations of Cl and Br . . . . . . . . . . 33
2.5.7 Indicators of the Presence of Heteroatoms . . . . . . . . . . . . . 34
2.5.8 Rules for Determining the Relative Molecular Weight (Mr) . . 36
2.5.9 Homologous Mass Series as Indications of Structural Type . . 37
2.5.10 Mass Correlation Table . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.5.11 Common Fragmentations of [M+H]+ in ESI- and
API-MS/MS-Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.5.12 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.6 UV/Vis Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
VII
VIII Table of Contents
3 Combination Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
3.1 Alkanes, Cycloalkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
3.2 Alkenes, Cycloalkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.3 Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.4 Aromatic Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3.5 Heteroaromatic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.6 Halogen Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.7 Oxygen Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.7.1 Alcohols and Phenols . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.7.2 Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3.8 Nitrogen Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.8.1 Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.8.2 Nitro Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3.9 Thiols and Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.10 Carbonyl Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.10.1 Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.10.2 Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.10.3 Carboxylic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.10.4 Esters and Lactones . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.10.5 Amides and Lactams . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4 13C NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
4.1 Alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
4.1.1 Chemical Shifts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
4.1.2 Coupling Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.1.3 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
4.2 Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
4.2.1 Chemical Shifts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
4.2.2 Coupling Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
4.2.3 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
4.3 Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
4.3.1 Chemical Shifts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
4.3.2 Coupling Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
4.3.3 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
4.4 Alicyclics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
4.4.1 Chemical Shifts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
4.4.2 Coupling Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
4.5 Aromatic Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
4.5.1 Chemical Shifts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
4.5.2 Coupling Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
4.5.3 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
Table of Contents IX
4.6 Heteroaromatic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
4.6.1 Chemical Shifts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
4.6.2 Coupling Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
4.7 Halogen Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
4.7.1 Fluoro Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
4.7.2 Chloro Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.7.3 Bromo Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
4.7.4 Iodo Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
4.7.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
4.8 Alcohols, Ethers, and Related Compounds . . . . . . . . . . . . . . . . . . . 120
4.8.1 Alcohols. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
4.8.2 Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
4.9 Nitrogen Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
4.9.1 Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
4.9.2 Nitro and Nitroso Compounds . . . . . . . . . . . . . . . . . . . . . 125
4.9.3 Nitrites and Nitrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
4.9.4 Nitrosamines and Nitramines . . . . . . . . . . . . . . . . . . . . . . 126
4.9.5 Azo and Azoxy Compounds . . . . . . . . . . . . . . . . . . . . . . . 126
4.9.6 Imines and Oximes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
4.9.7 Hydrazines, Hydrazones, and Carbodiimides . . . . . . . . . . . . 128
4.9.8 Nitriles and Isonitriles . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
4.9.9 Isocyanates, Thiocyanates, and Isothiocyanates . . . . . . . . . . 129
4.10 Sulfur Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
4.10.1 Thiols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
4.10.2 Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
4.10.3 Disulfides and Sulfonium Salts . . . . . . . . . . . . . . . . . . . . 131
4.10.4 Sulfoxides and Sulfones . . . . . . . . . . . . . . . . . . . . . . . . 132
4.10.5 Sulfonic and Sulfinic Acids and Derivatives . . . . . . . . . . . 133
4.10.6 Sulfurous and Sulfuric Acid Derivatives . . . . . . . . . . . . . . 133
4.10.7 Sulfur-Containing Carbonyl Derivatives . . . . . . . . . . . . . . 134
4.11 Carbonyl Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
4.11.1 Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
4.11.2 Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
4.11.3 Carboxylic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
4.11.4 Esters and Lactones . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
4.11.5 Amides and Lactams . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
4.11.6 Miscellaneous Carbonyl Derivatives . . . . . . . . . . . . . . . . 144
4.12 Miscellaneous Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
4.12.1 Compounds with Group IV Elements . . . . . . . . . . . . . . . . 146
4.12.2 Phosphorus Compounds . . . . . . . . . . . . . . . . . . . . . . . . 147
4.12.3 Miscellaneous Organometallic Compounds . . . . . . . . . . . . 149
X Table of Contents
4.13 Natural Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
4.13.1 Amino Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
4.13.2 Carbohydrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
4.13.3 Nucleotides and Nucleosides . . . . . . . . . . . . . . . . . . . . . 157
4.13.4 Steroids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
4.14 Spectra of Solvents and Reference Compounds . . . . . . . . . . . . . . . 160
4.14.1 13C NMR Spectra of Common Deuterated Solvents . . . . . . 160
4.14.2 13C NMR Spectra of Secondary Reference Compounds . . . 164
4.14.3 13C NMR Spectrum of a Mixture of Common
Nondeuterated Solvents . . . . . . . . . . . . . . . . . . . . . . . . 165
5 1H NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
5.1 Alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
5.1.1 Chemical Shifts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
5.1.2 Coupling Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
5.2 Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
5.2.1 Ethylenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
5.2.2 Conjugated Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
5.2.3 Allenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
5.3 Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
5.4 Alicyclics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
5.5 Aromatic Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
5.6 Heteroaromatic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
5.6.1 Non-Condensed Heteroaromatic Rings. . . . . . . . . . . . . . . . 194
5.6.2 Condensed Heteroaromatic Rings . . . . . . . . . . . . . . . . . . . 201
5.7 Halogen Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
5.7.1 Fluoro Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
5.7.2 Chloro Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
5.7.3 Bromo Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
5.7.4 Iodo Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
5.7.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
5.8 Alcohols, Ethers, and Related Compounds . . . . . . . . . . . . . . . . . . . 211
5.8.1 Alcohols. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
5.8.2 Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
5.9 Nitrogen Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
5.9.1 Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
5.9.2 Nitro and Nitroso Compounds . . . . . . . . . . . . . . . . . . . . . 218
5.9.3 Nitrites and Nitrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
5.9.4 Nitrosamines, Azo and Azoxy Compounds . . . . . . . . . . . . . 219
5.9.5 Imines, Oximes, Hydrazines, Hydrazones, and Azines . . . . . 220
5.9.6 Nitriles and Isonitriles . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
Table of Contents XI
5.9.7 Cyanates, Isocyanates, Thiocyanates, and Isothiocyanates . . . 222
5.10 Sulfur Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
5.10.1 Thiols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
5.10.2 Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
5.10.3 Disulfides and Sulfonium Salts . . . . . . . . . . . . . . . . . . . 225
5.10.4 Sulfoxides and Sulfones . . . . . . . . . . . . . . . . . . . . . . . . 225
5.10.5 Sulfonic, Sulfurous, and Sulfuric Acids and Derivatives . . . 226
5.10.6 Thiocarboxylate Derivatives . . . . . . . . . . . . . . . . . . . . . 226
5.11 Carbonyl Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
5.11.1 Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
5.11.2 Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
5.11.3 Carboxylic Acids and Carboxylates . . . . . . . . . . . . . . . . . 229
5.11.4 Esters and Lactones . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
5.11.5 Amides and Lactams . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
5.11.6 Miscellaneous Carbonyl Derivatives . . . . . . . . . . . . . . . . 235
5.12 Miscellaneous Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
5.12.1 Compounds with Group IV Elements . . . . . . . . . . . . . . . . 237
5.12.2 Phosphorus Compounds . . . . . . . . . . . . . . . . . . . . . . . . 238
5.12.3 Miscellaneous Compounds . . . . . . . . . . . . . . . . . . . . . . 241
5.12.4 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
5.13 Natural Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
5.13.1 Amino Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
5.13.2 Carbohydrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
5.13.3 Nucleotides and Nucleosides . . . . . . . . . . . . . . . . . . . . . 249
5.14 Spectra of Solvents and Reference Compounds . . . . . . . . . . . . . . . 251
5.14.1 1H NMR Spectra of Common Deuterated Solvents . . . . . . . 251
5.14.2 1H NMR Spectra of Secondary Reference Compounds . . . . 253
5.14.3 1H NMR Spectrum of a Mixture of Common
Nondeuterated Solvents . . . . . . . . . . . . . . . . . . . . . . . . 254
6 Heteronuclear NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . 255
6.1 15N NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
6.1.1 Heteroaromatic Compounds . . . . . . . . . . . . . . . . . . . . . . . 255
6.1.2 Amines and Ammonium Salts . . . . . . . . . . . . . . . . . . . . . 259
6.1.3 Carbonyl and Thiocarbonyl Derivatives . . . . . . . . . . . . . . . 261
6.1.4 Further Amine Derivatives . . . . . . . . . . . . . . . . . . . . . . . . 263
6.1.5 Compounds with C=N Bonds . . . . . . . . . . . . . . . . . . . . . . 265
6.1.6 Compounds with N=O Bonds . . . . . . . . . . . . . . . . . . . . . . 267
6.1.7 Compounds with Nitrogen-Nitrogen Multiple Bonds . . . . . . 268
6.1.8 Nitriles, Isonitriles, Cyanates, Isocyanates and Thio
Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269