Structure Determination of Organic Compounds: Tables of Spectral Data, Third Edition

E. Pretsch, P. Buhlmann, C. Affolter Structure Determination of Organic Compounds Tables of Spectral Data Third Complet...

Author: Ernö Pretsch | Philippe Bühlmann | Christian Affolter

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E. Pretsch, P. Buhlmann, C. Affolter

Structure Determination of Organic Compounds Tables of Spectral Data Third Completely Revised and Enlarged English Edition Corrected first Printing

Springer

Professor Emoe Pretsch ETH Zurich Laboratory of Organic Chemistry CH-8092Zurich Switzerland Dr. Philippe Biihlmann Department of Chemistry School of Science The University of Tokyo Hongo 7-3-1, Bunkyo-Ku Tokyo 113-0033 Japan Dr. Christian Affolter Aengerich 8 CH-3303 Muenchringen Switzerland

ISBN 3-540-678 15-8 Springer-Verlag Berlin Heidelberg New York CIP-Data applied for Pretsch, Ernoe: Structure determination of organic compounds : tables of spectral data / E. Pretsch ; P. Biihlmann ; C. Affolter. - 3., completely rev. and enl. engl. ed.. Berlin ; Heidelberg ; New York ; Barcelona ; Hong Kong ; London ; Milan ; Paris ; Singapore ; Tokyo : Springer, 2000 ISBN 3-540-67815-8 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in other ways, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution act under German Copyright Law. Springer-Verlag Berlin Heidelberg New York a member of BertelsmannSpringer Science+Business Media GmbH 0 Springer-Verlag Berlin Heidelberg 2000

Printed in Germany Copyright for the CD-ROM: Upstream Solutions GmbH, CH-6052 Hergiswil, Switzerland The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Typesetting: Camera-ready by editors Cover layout: design & production GmbH, Heidelberg Printed on acid-free paper SPIN: 10896235 52/3020 - 5 4 3 2 1 0 .

Preface

While modern techniques of nuclear magnetic resonance and mass spectrometry changed the ways of data acquisition and greatly extended the capabilities of these methods, the basic parameters, such as chemical shifts, coupling constants, and fragmentation pathways remain the same. This explains the ongoing success of the earlier editions of this book. However, since the amount of available data has considerably increased over the years, we decided to prepare an entirely new manuscript. It follows the same basic concepts, i.e., it provides a representative, albeit limited set of reference data for the interpretation of 13C NMR, 'H NMR, IR, mass, and UV/Vis spectra. On the other hand, the book has undergone a number of changes. The amount of reference data has been doubled at least (especially for MS and IR) and the order and selection of data for the various spectroscopic methods is now arranged strictly in the same way. In addition, the the enclosed compact disc contains programs for estimating NMR chemical shifts and generating isomers based on structural information. Unfortunately, our teachers and colleagues, Prof. Wilhelm Simon and Prof. Thomas Clerc are no longer among us, and Prof. Joseph Seibl has retired years ago. Their contributions to developing the concept and the earlier editions of this work cannot be overemphasized. We also thank numerous colleagues who helped us in many different ways to complete the manuscript. We are particularly indebted to Dr. Dorothee Wegmann for her expertise with which she eliminated many errors and inconsistencies of the first versions. Special thanks are due to Dr. Rich Knochenmuss (ETH Zurich) for the MALDI mass spectra of matrix materials, Dr. Kikuko Hayamizu for her help with the Spectral Database System of the National Institute of Materials and Chemical Research, Tsukuba, Ibaraki (Japan), Prof. Bernhard Jaun and Dr. Martin Badertscher (ETH Zurich) for critically reading parts of the manuscript. Dr. Martin Badertscher is also thanked for the tutorial of the structure generator, Assemble 2.0, and Upstream Solutions (Hergiswil, Switzerland) for providing free versions of the computer programs on the enclosed compact disk. In spite of great efforts and many checks to eliminate errors, it is likely that some errors or inconsistencies remain. We would like to encourage our readers to contact us with comments and suggestions or any kind of problems when using the book or the enclosed programs under one of the following addresses: Prof. Ern0 Pretsch, Laboratory of Organic Chemistry, CH-8092 Zurich, Switzerland, e-mail: [email protected], or Prof. Philippe Buhlmann, Department of Chemistry, University of Minnesota, 207 Pleasant St., SE, Minneapolis, MN 55455, USA, e-mail: [email protected]. Zurich and Tokyo, August 2000

Table of Contents

VII

Table of Contents

1 Introduction .........................................................................

1

Scope and Organization ........................................................ Abbreviations and Symbols ..................................................

1 3

2 Summary Tables ..................................................................

5

1.1 1.2

2.1

2.2 2.3 2.4 2.5

2.6

General Tables .................................................................... 2.1.1 Calculation of the Number of Double Bond Equivalents from the Molecular Formula ..................................... 2.1.2 Properties of Selected Nuclei ..................................... 13c NMR Spectroscopy ...................................................... lH NMR Spectroscopy ........................................................ IR Spectroscopy ................................................................. Mass Spectrometry .............................................................. 2.5.1 Average Masses of Naturally Occurring Elements with Exact Masses and Representative Relative Abundances of Isotopes ................................................................ Ranges of Natural Isotope Abundances of Selected 2.5.2 Elements ............................................................... Isotope Patterns of Naturally Occurring Elements ......... 2.5.3 Calculation of Isotope Distributions........................... 2.5.4 Isotopic Abundances of Various Combinations of 2.5.5 Chlorine. Bromine. Sulfur. and Silicon ....................... Isotope Patterns of Combinations of C1 and Br ............. 2.5.6 Indicators of the Presence of Heteratoms ...................... 2.5.7 Rules for Determining the Relative Molecular Weight 2.5.8 (Mr) ..................................................................... Homologous Mass Series as Indications of Structural 2.5.9 Type .................................................................... 2.5.10 Mass Correlation Table ............................................ 2.5.11 References ............................................................. UVNis Spectroscopy ..........................................................

5 5 6 7 10 13 18 18 24 25 26 28 30 31 33 34 36 46 47

3 Combination Tables ............................................................

49

Alkanes. Cycloalkanes ......................................................... Alkenes. Cycloalkenes ......................................................... Alkynes ............................................................................ Aromatic Hydrocarbons ........................................................ Heteroaromatic Compounds ..................................................

49 50 51 52 53

3.1 3.2 3.3 3.4 3.5

Vlll

Table of Contents

Halogen Compounds ........................................................... Oxygen Compounds ............................................................ 3.7.1 Alcohols and Phenols .............................................. 3.7.2 Ethers ................................................................... 3.8 Nitrogen Compounds....................... ................................ 3.8.1 Amines ................................................................. 3.8.2 Nitro Compounds ................................................... 3.9 Thiols and Sulfides .............................................................. 3.10 Carbonyl Compounds.......................................................... 3.10.1 Aldehydes .............................................................. 3.10.2 Ketones ................................................................ 3.10.3 Carboxylic Acids .................................................... 3.10.4 Carboxylic Esters and Lactones ................................. 3.10.5 Carboxylic Amides and Lactams ................................ 3.6 3.7

4 13C NMR Spectroscopy ..................................................... 4.1

4.2

4.3

4.4

4.5

4.6 4.7

4.8

Alkanes ............................................................................. 4.1.1 Chemical Shifts ..................................................... 4.1.2 Coupling Constants ................................................ 4.1.3 References ............................................................. Alkenes ............................................................................. 4.2.1 Chemical Shifts ..................................................... 4.2.2 Coupling Constants ................................................ 4.2.3 References ............................................................. Alkynes ............................................................................ 4.3.1 Chemical Shifts ..................................................... 4.3.2 Coupling Constants ................................................ 4.3.3 References ............................................................. Alicyclics .......................................................................... 4.4.1 Chemical Shifts ..................................................... 4.4.2 Coupling Constants ................................................ 4.4.3 References ............................................................. Aromatic Hydrocarbons ........................................................ 4.5.1 Chemical Shifts ..................................................... 4.5.2 Coupling Constants ................................................ 4.5.3 References ............................................................. Heteroaromatic Compounds .................................................. 4.6.1 Chemical Shifts ..................................................... 4.6.2 Coupling Constants ................................................ Halogen Compounds ........................................................... 4.7.1 Fluoro Compounds. ................................................ 4.7.2 Chloro Compounds ................................................. 4.7.3 Bromo Compounds ................................................. 4.7.4 Iodo Compounds .................................................... 4.7.5 References ............................................................. Alcohols. Ethers. and Related Compounds ............................... 4.8.1 Alcohols ............................................................... 4.8.2 Ethers ...................................................................

54 56 56 57 59 59 60 62 63 63 64 65 66 68 71 71 71 80 81 82 82 86 87 88 88 89 89 90 90 95 95 96 96 102 103 104 104 111 112 112 114 115 116 116 117 117 119

Table of Contents

4.9

4.10

4.1 1

4.12

4.13

4.14

5

Nitrogen Compounds ........................................................... 4.9.1 Amines ................................................................. 4.9.2 Nitro and Nitroso Compounds ................................... 4.9.3 Nitrosamines ......................................................... 4.9.4 Imines and Oximes ................................................. 4.9.5 Hydrazones and Carbodiimides ................................... 4.9.6 Nitriles and Isonitriles ............................................. 4.9.7 Isocyanates. Thiocyanates and Isothiocyanates .............. 4.9.8 References............................................................. Sulfur-Containing Functional Groups ..................................... 4.10.1 Thiols .................................................................. 4.10.2 Sulfides ................................................................ 4.10.3 Disulfides and Sulfonium Salts ................................. 4.10.4 Sulfoxides and Sulfones ........................................... 4.10.5 Sulfonic and Sulfinic Acids and Derivatives ................. 4.10.6 Sulfurous and Sulfuric Acid Derivatives...................... 4.10.7 Sulfur-Containing Carbonyl Derivatives ..................... Carbonyl Compounds .......................................................... 4.11.1 Aldehydes .............................................................. 4.11.2 Ketones ................................................................ 4.1 1.3 Carboxylic Acids and Carboxylates ............................ 4.1 1.4 Esters and Lactones ................................................. 4.1 1.5 Amides and Lactams ................................................ 4.11.6 Miscellaneous Carbonyl Derivatives ........................... Miscellaneous Compounds ................................................... 4.12.1 Derivatives of Group IV Elements ............................. 4.12.2 Phosphorus Compounds .......................................... 4.12.3 Miscellaneous Organometallic Compounds .................. Natural Products ................................................................. 4.13.1 Amino Acids ......................................................... 4.13.2 Carbohydrates ........................................................ 4.13.3 Nucleotides and Nucleosides ...................................... 4.13.4 Steroids ................................................................ Spectra of Solvents and Reference Compounds ......................... 4.14.1 3C NMR Spectra of Common Deuterated Solvents ..... 4.14.2 I3C NMR Spectra of Secondary Reference Compounds . 4.14.3 13C NMR Spectrum of a Mixture of Common Nondeuterated Solvents ............................................

H NMR Spectroscopy ....................................................... 5.1

5.2 5.3

Alkanes ............................................................................. 5.1.1 Chemical Shifts ..................................................... 5.1.2 Coupling Constants ................................................ 5.1.3 References............................................................. Alkenes ............................................................................. 5.2.1 Substituted Ethylenes .............................................. 5.2.2 Dienes .................................................................. Alkynes ............................................................................

IX

121 121 123 124 124 125 126 127 127 128 128 128 130 130 131 131 132 133 133 134 136 138 140 142 144 144 145 147 148 148 152 154 156 157 157 159 160 161 161 161 166 167 168 168 174 175

Table of Contents

X

5.4 5.5 5.6 5.7

5.8 5.9

5.10

5.1 1

5.12

5.13

5.14

Chemical Shifts and Coupling Constants .................... 5.3.1 Alicyclics .......................................................................... Aromatic Hydrocarbons ........................................................ Heteroaromatic Compounds .................................................. 5.6.1 Non-Condensed Heteroaromatic Rings ........................ 5.6.2 Condensed Heteroaromatic Rings ............................... Halogen Compounds ........................................................... 5.7.1 Fluoro Compounds ................................................. 5.7.2 Chloro Compounds ................................................. 5.7.3 Bromo Compounds ................................................. 5.7.4 Iodo Compounds .................................................... Alcohols, Ethers, and Related Compounds ............................... 5.8.1 Alcohols ............................................................... 5.8.2 Ethers ................................................................... Nitrogen Compounds ........................................................... 5.9.1 Amines ................................................................. 5.9.2 Nitro and Nitroso Compounds .................................. 5.9.3 Nitrosamines, Azo, and Azoxy Compounds ................. 5.9.4 Imines, Oximes, Hydrazones, and Azines .................... 5.9.5 Nitriles and Isonitriles ............................................. 5.9.6 Cyanates, Isocyanates, Thiocyanates, and Isothiocyanates Sulfur-Containing Functional Groups ..................................... 5.10.1 Thiols .................................................................. 5.10.2 Sulfides ................................................................ 5.10.3 Disulfides and Sulfonium Salts ................................. 5.10.4 Sulfoxides and Sulfones ........................................... 5.10.5 Sulfonic, Sulfinic, Sulfurous, and Sulfuric Acids and Derivatives ............................................................ 5.10.6 Thiocarboxylate Derivatives ...................................... Carbonyl Compounds .......................................................... 5.1 1.1 Aldehydes .............................................................. 5.1 1.2 Ketones ................................................................ 5.1 1.3 Carboxylic Acids and Carboxylates ............................ 5.1 1.4 Esters and Lactones ................................................. 5.1 1.5 Amides and Lactams ................................................ 5.1 1.6 Miscellaneous Carbonyl Derivatives ........................... Miscellaneous Compounds ................................................... 5.12.1 Silicon Compounds ................................................ 5.12.2 Phosphorus Compounds .......................................... 5.12.3 Miscellaneous Compounds ....................................... Natural Products ................................................................. 5.13.1 Amino Acids ......................................................... 5.13.2 Carbohydrates ........................................................ 5.13.3 Nucleotides and Nucleosides ...................................... 5.13.4 References ............................................................. Spectra of Solvents and Reference Compounds ......................... 5.14.1 H NMR Spectra of Common Deuterated Solvents ....... 5.14.2 1H NMR Spectra of Secondary Reference Compounds ...

*

175 176 180 186 186 193 198 198 199 200 201 202 202 204 207 207 210 210 211 212 213 214 214 215 216 216 217 217 218 218 219 220 221 223 226 228 228 229 232 233 233 236 237 239 240 240 242

Table of Contents

5.14.3

XI .

1H NMR Spectrum of a Mixture of Common Nondeuterated Solvents ............................................

243

6 IR Spectroscopy..................................................................

245

Alkanes ............................................................................. Alkenes ............................................................................. 6.2.1 Monoenes ............................................................. 6.2.2 Allenes ................................................................. 6.3 Alkynes ............................................................................ 6.4 Alicyclics .......................................................................... 6.5 Aromatic Hydrocarbons ........................................................ 6.6 Heteroaromatic Compounds .................................................. 6.7 Halogen Compounds ........................................................... 6.7.1 Fluoro Compounds ................................................. 6.7.2 Chloro Compounds ................................................. 6.7.3 Bromo Compounds ................................................. 6.7.4 Iodo Compounds .................................................... 6.8 Alcohols, Ethers, and Related Compounds ............................... 6.8.1 Alcohols and Phenols., ............................................ 6.8.2 Ethers, Acetals, Ketals ............................................. 6.8.3 Epoxides ............................................................... 6.8.4 Peroxides and Hydroperoxides .................................... 6.9 Nitrogen Compounds ........................................................... 6.9.1 Amines and Related Compounds ................................ 6.9.2 Nitro and Nitroso Compounds ................................... 6.9.3 Imines and Oximes ................................................. 6.9.4 Azo Compounds ..................................................... 6.9.5 Nitriles and Isonitriles ............................................. 6.9.6 Diazo Compounds .................................................. 6.9.7 Cyanates and Isocyanates .......................................... 6.9.8 Thiocyanates and Isothiocyanates ............................... 6.10 Sulfur-Containing Functional Groups ..................................... 6.10.1 Thiols and Sulfides ................................................. 6.10.2 Sulfoxides and Sulfones ........................................... 6.10.3 Thiocarbonyl Derivatives ......................................... 6.10.4 Thiocarbonic Acid Derivatives ................................... 6.1 1 Carbonyl Compounds .......................................................... 6.1 1.1 Aldehydes .............................................................. 6.1 1.2 Ketones ................................................................ 6.1 1.3 Carboxylic Acids .................................................... 6.1 1.4 Esters and Lactones ................................................. 6.1 1.5 Armdes and Lactames .............................................. 6.1 1.6 Acid Anhydrides ..................................................... 6.1 1.7 Acid Halides .......................................................... 6.1 1.8 Carbonic Acid Derivatives ........................................ 6.12 Miscellaneous Compounds ................................................... 6.12.1 Silicon Compounds ................................................ 6.12.2 Phosphorus Compounds ..........................................

245 248 248 251 252 253 255 258 260 260 261 262 262 263 263 264 266 267 268 268 270 272 274 275 276 277 278 280 280 281 283 283 286 286 287 290 292 295 298 300 301 304 304 305

6.1 6.2

Table of Contents

XI1

6.12.3 Boron Compounds .................................................. 6.13 Amino Acids ...................................................................... 6.14 Solvents. Suspension Media. and Interferences .......................... 6.14.1 Infrared Spectra of Common Solvents ......................... 6.14.2 Infrared Spectra of Suspension Media .......................... 6.14.3 Interferences in Infrared Spectra ..................................

308 309 310 310 311 312

7 Mass Spectrometry .............................................................

313

7.1

7.2

7.3 7.4

7.5

7.6

7.7

Alkanes ............. ............................................................ 7.1.1 Unbranched Alkanes ................................................ 7.1.2 Branched Alkanes .................................................... 7.1.3 References ............................................................. Alkenes ............................................................................. 7.2.1 Unbranched Alkenes ................................................ 7.2.2 Branched Alkenes .................................................... 7.2.3 Polyenes and Polyynes ............................................ 7.2.4 References ............................................................. Alkynes ....................................................................... 7.3.1 Aliphatic Alkynes ................................................... 7.3.2 References ............................................................. Alicyclic Hydrocarbons ............ ..................................... 7.4.1 Cyclopropanes ....................................................... 7.4.2 Saturated Monocyclic Alicyclics ................................ 7.4.3 Polycyclic Alicyclics ............ ............................... 7.4.4 Cyclohexenes ......................................................... 7.4.5 References ............................................................. Aromatic Hydrocarbones ....................................................... 7.5.1 Aromatic Hydrocarbons ............................................ 7.5.2 Alkylsubstituted Aromatic Hydrocarbons ..................... 7.5.3 References ...................... .................................. Heteroaromatic Compounds .................................................. 7.6.1 General Characteristics ............................................. 7.6.2 Furans .................................................................. 7.6.3 Thiophenes ............................................................ 7.6.4 Pyrroles ................................................................ 7.6.5 Pyridines ............................................................... 7.6.6 N-Oxides of Pyridines and Quinolines......................... 7.6.7 Pyridazines and Pyrimidines ............................... 7.6.8 Pyrazines ...... ....................................... 7.6.9 Indoles .................................................................. 7.6.10 Quinolines ............................................................ 7.6.1 1 Cinnoline .............................................................. 7.6.12 References ........... ............................................. Halogen ............................................................................ 7.7.1 Saturated Aliphatic Halides ....................................... 7.7.2 Polyhaloalkanes ..................................................... 7.7.3 Aromatic Halides .................................................... 7.7.4 References .............................................................

313 313 313 314 315 15 315 316 316 317 317 317 318 318 319 319 319 320 321 321 321 322 323 323 323 323 324 324 325 325 326 326 326 327 327 328 328 329 329 329

Table of Contents

Alcohols ........................................................................... 7.8.1 Aliphatic Alcohols .................................................. 7.8.2 Alicyclic Alcohols .................................................. 7.8.3 Unsaturated Aliphatic Alcohols ................................. 7.8.4 Vicinal Glycols., .................................................... 7.8.5 Aliphatic Hydroperoxides ......................................... Phenols ................................................................ 7.8.6 7.8.7 Benzyl .................................................................. 7.8.8 Aliphatic Ethers ..................................................... Unsaturated Ethers .................................................. 7.8.9 7.8.10 Alkyl Cycloalkyl Ethers .......................................... 7.8.11 Cyclic Ethers ......................................................... 7.8.12 Aliphatic Epoxides .................................................. 7.8.13 Methox ybenzenes ................................................... 7.8.14 Alkyl Aryl Ethers ................................................... 7.8.15 Aromatic Ethers ..................................................... 7.8.16 Aliphatic Peroxides ................................................. 7.8.17 References ............................................................. 7.9 Nitrogen Compounds........................................................... 7.9.1 Saturated Aliphatic Amines ...................................... 7.9.2 Cycloalkylamines ................................................... 7.9.3 Cyclic Amines ....................................................... 7.9.4 Piperazines ............................................................ 7.9.5 Aromatic Amines ................................................... 7.9.6 Aliphatic Nitro Compounds ...................................... 7.9.7 Aromatic Nitro Compounds ...................................... 7.9.8 Diazo ................................................................... 7.9.9 Azobenzenes .......................................................... 7.9.10 Aliphatic Azides ..................................................... 7.9.1 1 Aromatic Azides ..................................................... 7.9.12 Aliphatic Nitriles .................................................... 7.9.13 Aromatic Nitriles .................................................... 7.9.14 Aliphatic Isonitriles (R-NC) ..................................... 7.9.15 Aromatic Isonitriles (R-NC) ..................................... 7.9.16 Aliphatic Cyanates (R-OCN) .................................... 7.9.17 Aromatic Cyanates (R-OCN) .................................... 7.9.18 Aliphatic Isocyanates (R-NCO) ................................. 7.9.19 Aromatic Isocyanates (R-NCO) ................................. 7.9.20 Aliphatic Thiocyanates (R-SCN) ............................... 7.9.21 Aromatic Thiocyanates (R-SCN) ............................... 7.9.22 Aliphatic Isothiocyanates (R-NCS) ............................ 7.9.23 Aromatic Isothiocyanates (R-NCS) ............................ 7.9.24 References ............................................................. 7.10 Sulfur-Containing Functional Groups ..................................... 7.10.1 Aliphatic Thiols ..................................................... 7.10.2 Aromatic Thiols ..................................................... 7.10.3 Aliphatic Sulfides ................................................... 7.10.4 Alkyl Vinyl Sulfides ............................................... 7.10.5 Cyclic Sulfides .......................................................

7.8

Xlll

330 330 331 331 331 332 332 332 333 334 335 335 336 337 337 337 337 338 339 339 339 340 341 341 341 342 342 342 342 343 343 344 344 344 345 345 345 346 346 347 347 347 348 349 349 349 350 350 351

XIV

Table of Contents

7.10.6 Aromatic Sulfides ................................................... 7.10.7 Disulfides .............................................................. 7.10.8 Aliphatic Sulfoxides ................................................ 7.10.9 Alkyl Aryl and Diaryl Sulfoxides ............................... 7.10.10 Aliphatic Sulfones .......................................... 7.10.1 1 Cyclic Sulfones...................................................... 7.10.12 Alkyl Aryl Sulfones ................................................ 7.10.13 Diaryl Sulfones ...................................................... 7.10.14 Aromatic Sulfonic Acids .......................................... 7.10.15 Alkylsulfonic Acid Esters ......................................... 7.10.16 Arylsulfonic Acid Esters .......................................... 7.10.17 Aromatic Sulfonamides ............................................ 7.10.18 Thiocarboxylic Acid S-Esters .................................... 7.10.19 References ............................................................. 7.11 Carbonyl Compounds .......................................................... 7.1 1.1 Aliphatic Aldehydes ................................................ 7.1 1.2 Unsaturated Aliphatic Aldehydes ................................ 7.1 1.3 Aromatic Aldehydes ................................................ 7.1 1.4 Aliphatic Ketones ................................................... 7.1 1.5 Unsaturated Ketones ................................................ 7.1 1.6 Alicyclic Ketones ................................................... 7.1 1.7 Aromatic Ketones ................................................... 7.11.8 Aliphatic Carboxylic Acids .................... ........ 7.1 1.9 Aromatic Carboxylic Acids ....... ........................ 7.1 1.10 Carboxylic Acid Anhydrides ...................................... 7.11.11 Saturated Aliphatic Esters ......................................... 7.11.12 Unsaturated Esters ................................................... 7.1 1.13 Esters of Aromatic Acids ........... ........................... 7.1 1.14 Lactones ................................... ........................ 7.1 1.15 Aliphatic Amides .................................................... 7.1 1.16 Amides of Aromatic Carboxylic Acids ........................ 7.1 1 . 17 Anilides ................................................................ 7.1 1.18 Lactams ................................................................ 7.1 1.19 Imides .................................................. 7.1 1.20 References ............................................................. 7.12 Miscellaneous Compounds ................................................... 7.12.1 Trialkylsilyl Ethers .............. ............................... 7.12.2 Alkyl Phosphates ................................................... 7.12.3 Aliphatic Phosphines .............................................. 7.12.4 Aromatic Phosphines and Phosphine Oxides .... 7.12.5 References ............................................................. 7.13 Mass Spectra of Common Solvents and Matrix Compounds ....... 7.13.1 Electron Impact Ionization Mass Spectra of Common Solvents ............................................................... 7.13.2 Spectra of Common FAB MS Matrix and Calibration Compounds ........................................................... 7.13.3 Spectra of Common MALDI MS Matrix Compounds ... 7.1 3.4 References .............................................................

351 351 352 352 353 354 354 355 355 355 356 356 357 357 358 358 358 358 359 359 359 360 360 361 361 361 362 363 364 364 365 365 365 367 368 369 369 369 369 370 370 371 371 374 380 383

Table of Contents

8 UV/Vis Spectroscopy .............................................. 8.1 8.2 8.3 8.4

8.5

8.6

Correlation Between Wavelength of Absorbed Radiation and Observed Color ..... ............................. UV/Vis Absorption o mophores .......................... UV/Vis Absorption of Conjugated Alkenes ................ 8.3.1 UV Absorption of Dienes and Polyenes ...................... 8.3.2 UV Absorption of a$-Unsaturated Carbonyl Compounds UVNis Absorption of Aromatic Compounds ........................... 8.4.1 UV Absorption of Monosubstituted Benzenes .............. 8.4.2 UV Absorption of Substituted Benzenes 8.4.3 UV Absorption of Aromatic Carbonyl Compounds ....... UV/Vis Reference Spectra ..................................................... 8.5.1 UVNis Spectra of Alkenes and Alkynes ..................... 8.5.2 UVNis Spectra of Aromatic Compounds .................... 8.5.3 UVNis Spectra of Heteroaromatic Compounds ............ 8.5.4 UVNis Spectra of Miscellaneous Compounds ............. 8.5.5 UVNis Spectra of Nucleotides .................................. UVNis Absorption of Common Solvents ...............................

Subject index ...........................................................................

xv 385

385 385 387 387 388 390 390 39 1 392 393 393 394 399 401 403 404 406

SUBJECT INDEX

Index Terms

Links

A Acenaphthene

C96

H181

Acenaphthylene

C96

H181

Acetaldehyde

C133

H218

Acetaldoxime

H211

I274

I287

N/N-Acetals

11

O/O-Acetals

4

9

C120

H206

I245

I246

I264

I265

– methyl

41

O/S-Acetals

8

9

Acetamides

37

C140

H224

Acetanilides

M365

Acetate ion

C137 37

39

I291

I293

C137

H220

I291

M371

H226

I299

C81

C134

C160

H243

M371

U405

Acetates Acetic acid

U403 – esters

C138

– anhydride

C142

Acetoisonitrile

C126

Acetone – dimethylhydrazone

C125

Acetone-d6

C157

H240

Acetonitrile

C126

C160

M371

U405

C157

H240

Acetonitrile-d3

H212

H219

H243

This page has been reformatted by Knovel to provide easier navigation.

Index Terms Acetophenone

Links C135

H219

M390

M397

Acetyl bromide

C142

H226

N-Acetyl-γ-butyrolactam

H227

Acetyl chloride

C142

– iodide

C142

N-Acetyl pyrrolidine

H225

N-Acetyl-γ-valerolactam

H227

Acetylacetone

C118

Acetylene Acetylenes

I289

M360

C135

H220

I289

C88

C89

H175

3

10

32

33

35

45

51

C88

H175

I246

I252

M317

32

40

H226

M385 – aliphatic

M317

Acetylenic ethers

M334

Acid – bromides

I300

– chlorides

4

6

46

I300

– fluorides

I300

– halides

C142

– iodides

I300

Acids

H226

I300

3

4

6

7

9

10

11

12

14

15

32

33

34

38

40

45

65

C136

C137

H220

I290

U386

– aliphatic

M360

– aromatic

M361


Index Terms

Links

Acids (Cont.) – α-methyl

41

– α,β-unsaturated

U388

Acridine

C110

H197

Acrylaldehyde

C133

H218

Acrylate ion

C137

Acrylic acid

C137

Acryloisonitrile

C126

Acrylonitrile

U401

H221

I251

C126

H212

I251

– chloride

C142

H226

– fluoride

H226

N-Acyl-piperidine

H225

Acryloyl

Adamantane

C94

H177

Adenine

C154

H238

Adenosine

C155

H238

Alanine

C148

H233

I292

β-Alanine

C148 4

7

10

32

33

34

40

42

45

56

C117

H202

I263

M330

U386

– alicyclic

32

37

M331

– aliphatic

C117

H202

M330

– primary

36

38

M330

– tertiary

34 4

6

9

12

14

32

34

35

40

42

45

63

C133

H218

I245

I286

Alcohols

– unsaturated Aldehydes

U404

M331


Index Terms Aldehydes (Cont.)

Links M358

– aliphatic

37

– allyl

35

– aromatic

M358

– α-methyl

39


U388

Aldimines

C124

H211

I273

Aldoximes

4

C125

H211

Alicyclic – alcohols

M331

– ketones

32

35

C135

H219

H220

M359

32

37

40

42

C90

H176

I247

I253

37

41

Alicyclics

C136

M318 – condensed

C94

– polycyclic

32

33

C94

M319

C117

H202

C85

H174

C145

H229

3

7

10

32

39

40

42

43

49

C71

H161

I245

M313

U385

Aliphatic – alcohols – dienes – phosphorus compounds Alkanes

– aromatically substituted

H165

– branched

M313

– cyclic

M330

32

37

40

42

50

C90

H176

I247

I253

M318


Index Terms – halogen-substituted – monosubstituted – polycyclic

Links M328 C74

H162

H163

32

33

37

41

4

7

8

10

32

37

40

41

42

45

50

C82

H168

I246

I248

M315

33

I253

3

10

32

33

35

45

51

C88

H175

I246

I252

M317

C86

H174

I251

M319 – unbranched Alkenes

M313

U385 – branched

M315

– conjugated

U387

– cyclic

32

– unbranched Alkynes

M315

U385 – aliphatic Allenes

M317 C85 U385

Allophanates

M303

Allyl – alcohols – aldehydes

C118

M331

35

– cyanide

M318

– ethers

M334

– methyl ether

C119

Allylamine

C122

Allylic couplings

H169

Amide protons

H223


Index Terms Amides

Links 3

4

7

8

9

14

15

32

39

45

68

C140

H223

I295

– aliphatic

M364

– of aromatic carboxylic acids

M365

– primary

I295

– secondary

I295

– tertiary

I295

Amine protons Amines

– aliphatic – alkenylsubstituted

H207 3

7

8

9

10

32

34

37

38

39

45

59

C121

H207

I245

I268

I312

M386

40

42

I269

M339

H209

M340

I251

– aromatic

M341

– benzylic

M341

– cyclic

C123

– cycloalkyl

M339

– methyl – primary – protonation induced shifts

36 I268

I269

C121

– secondary

I268

Amino acids

15

C148

M380

M382

10

C121

3-Aminoquinoline

H233

I309

H208

I268

Ammonium – compounds – ion

H208

– protons

H207


Index Terms

Links

5α-Androstane

C156

5β-Androstane

C156

Anhydrides

6

11

14

C142

H226

I298

M361

– cyclic

11

12

Anilides

M365

Anilines

8

33

37

42

43

C122

H209

U390

H180

H206

I266

H180

U398

U395 – alkylsubstituted Anisole

43 C119 U395

Anthracene

C96

Anthraquinone

I290

Antimony compounds

C99

C147

4

7

8

9

33

35

37

41

42

43

46

52

C96

H180

I255

M321

46

52

M321

C151

H234

C119

H206

M337

4

7

8

9

33

35

37

41

42

43

46

52

C96

H180

I255

M321

46

52

M321

Arenes

– condensed Arginine Aromatic – ethers – hydrocarbons

– – condensed – phosphorus compounds Arsenic compounds Aspartic acid

C146 C99

C147

C150

H234


Index Terms

Links

7-Azaindole

C109

Azepane

C123

Azetidine

C123

H209

Azides – aliphatic

M342

– aromatic

M343

Azines

H211

Aziridines

7

C123

Azo compounds

H210

I274

Azobenzenes

H211

M342

Azomethane

H211

Azoxy compounds

H210

Azulene

H209 U396

I274

C96

B Benzaldehydes Benzanthracene Benzene

C133

H218

U392

U397

I287

U390

U398 C96

C102

C160

H180

H243

I257

M372

U390

U394

U405

Benzene-1,3-diol

C118

Benzene-d6

C157

H240

M372

4

7

8

9

33

37

42

43

H182

U390

H217

M356

Benzenes

46 – halogen-substituted

I261

– monosubstituted

C97

– mulitiply substituted – perhalogenated Benzenesulfonamide

U391 40 C131


Index Terms

Links

Benzenesulfonic acid

C131

H217

– methyl ester

H217

Benzenesulfonyl chloride

C131

H217

Benzenethiol

C128

H214

Benzimidazole

C109

H193

Benzoate – ion

C137

– methyl

I294

Benzoates

I291

1,3-Benzodioxolane

C120

H206

Benzoic acid

C137

H221

I292

U390

H212

I275

U390

H219

I289

U397

U397 – esters

U392

– substituted

U392

Benzoic anhydride

C142

Benzoisonitrile

C126

Benzonitrile

C126

I299

U396 Benzophenone γ-Benzopyrones

C135 43

1,2-Benzoquinone

C136

I290

U397

1,4-Benzoquinone

C136

H220

I290

U397

14

35

C136

I288

Benzoquinones

I289 2,1,3-Benzothiadiazole

C109

H194

Benzothiazole

C109

H194

Benzotriazole

H194

2,1,3-Benzoxadiazole

C109

H194

Benzoxazole

C109

H193

Benzoxazoles

C109


Index Terms

Links

Benzoyl – chloride – derivatives

C142

H226

43

Benzo[l,4]dioxin

H195

Benzo[l,4]dithiin

H195

Benzo[b]furan

C109

H193

Benzo[b]thiophene

C109

H193

– alcohols

C118

H203

– bromide

C115

– chloride

C114

– fluoride

C113

Benzyl

– groups

9

– iodide

C116

– mercaptan

I264

M332

I280

– vinyl sulfide

C129

Benzylamine

C123

Benzylic amines

M341

N-Benzylideneaniline

C124

H211

N-Benzylidenemethylamine

C124

H211

Benzylthiol

C128

Bicyclo[2,2,2]octane

C94

Bicyclo[3,l,0]hexane

C94


C94

Bicyclo[4,l,0]heptane

C94


C94

Bicyclo[4,3,0]nonane

C94

Biphenyls

M321

2,2-Bis(ethylthio)propane

C129

Bis(isopropyloxy)methylphosphine

H230

Bis(tert-butylthio)methane

C129

U394


Index Terms

Links

Boranes

10

I308

Borates

10

I308

Boric acid esters Boron compounds

I308 10

C147

H178

H232

26

28

30

41

42

45

54

C115

H200

I262

U385

– aliphatic

44

M328

– aromatic

I262

M329

26

28

30

41

42

45

54

C115

H200

I262

U385

– aliphatic

44

M328

– aromatic

I262

M329

I308 Bromides

Bromo compounds

Bromoacetic acid

C115

Bromoacetone

C135

Bromoacetylene

H200

Bromoalkanes

M328

Bromobenzenes

C115

H200

Bromocyclohexane

C115

H200

Bromocyclopropane

C90

H200

Bromoethane

C115

H200

Bromoethylene

C115

H200

Bromoform

C115

H200

Bromoform-d

C157

H240

Bromomethane

C115

H200

Bromopropanes

C115

H200

Bromopyridines

C115

N-Bromosuccinimide

H227

I298

C85

C87

1,3-Butadiene

I261

U401

H174


Index Terms

Links

Butadiyne

C89

Butane

C71

H161

2,3-Butanedione

C135

1-Butanethiol

C128

H214

tert-Butanol

C117

H203

C81

C117

1-Butanol 2-Butanone

C134

Butenes

H168

N-Butylacetamide

H225

N-tert-Butylacetamide

C141

H225

– acetate

H221

I294

– group

H163

– isocyanate

C127

– isothiocyanate

C127

– methyl ethers

C119

– methyl ketones

C134

– methyl sulfides

C129

H215

– acetate

C138

H221

– cyanide

C126

H212

– dimethylamine

C122

– disulfides

H216

– fluoride

H198

I264

Butyl

I279

tert-Butyl

– group

C75

– methyl sulfone

C130

S-Butyl thioacetate

C132

Butylamine

H208

Butyldichlorophosphine

C145

Butyldimethylphosphine

C145

Butyldimethylphosphine sulfide

C146

H163


Index Terms

Links

tert-Butylamine

C121

tert-Butylbenzene

H181

tert-Butylbromide

C115

H200

tert-Butylchloride

C114

H199

tert-Butylfluoride

C112

tert-Butyliodide

C116

H201

C89

H175

Butyraldehydes

C133

H218

Butyric acid

C137

H221

– anhydride

C142

I299

γ-Butyrolactam

C141

H225

γ-Butyrolactone

C139

H223

I293

Butyronitrile

C126

Butynes

C 12

C NMR Spectroscopy

C71

Calibration compounds for MS

M374

ε-Caprolactone

C139

Carbaldehydes

4

6

12

14

32

34

35

40

42

45

63

C133

H218

I245

I286

M358

12

14

C143

H227

I301

I302

Carbamates – phenyl Carbazole

43 C110

H197

Carbodiimides

C92

C125

Carbohydrates

C152

H236

C143

I312

U386

Carbon – dioxide


Index Terms

Links

Carbon (Cont.) – disulfide

C143

C160

I311

M372

I310

I312

U405 – monoxide

C143

– tetrabromide

C115

– tetrachloride

C114

C160

M373

U405

– tetrafluoride

C112

– tetraiodide

C116

Carbonate ion

C143

Carbonic acid derivatives

11

12

14

15

C143

H227

I285

I301

63

C133

H218

I286

M358

M386

I302 Carbonyl compounds – α,β-unsaturated

U388

Carbonyl groups

6

10

11

Carboxamides

3

4

6

7

8

9

14

15

32

39

45

68

C140

H223

I295

15

C136

C137

H220

I290

U386

6

11

14

C142

H226

I298

M361

– aliphatic

M364

– of aromatic carboxylic acids

M365

– primary

I295

– secondary

I295

– tertiary

I295

Carboxyl protons Carboxylate anions Carboxylic acid anhydrides

H220


Index Terms

Links

Carboxylic acid anhydrides (Cont.) – cyclic

11

12

3

4

6

7

8

9

12

14

15

32

33

40

42

43

66

C138

H221

I292

U386

– of aromatic acids

65

M363

– ethyl

35

38

42

– methyl

36

39

41

C138

Carboxylic acid esters

I293 – phenyl

42

I293

– propyl

37

39

– saturated

M361

– unsaturated

M362

– α,β-unsaturated – vinyl

65

U388

I293

Carboxylic acids

3

4

6

7

9

10

11

12

14

15

32

33

34

38

40

45

65

C136

C137

H220

I290

U386

– aliphatic

M360

– aromatic

M361

– α-methyl

41

– α,β-unsaturated Catechol Chlorides

U388 I257

I264

3

4

8

9

26

28

29

33

36

38

40

41


Index Terms

Links

Chlorides (Cont.)

– aliphatic – aromatic Chloro compounds

– aliphatic – aromatic

45

54

C114

I261

M373

U385

3

4

8

9

32

42

54

M328

I261

M329

3

4

8

9

26

28

29

33

36

38

40

41

45

54

C114

H199

I261

M373

U385

3

4

8

9

32

42

54

M328

I261

M329

9

Chloroacetate ion

C137

Chloroacetic acid

C114

Chloroacetone

C135

Chloroacetylene

H199

Chloroalkanes Chlorobenzenes

H199

C137

3

4

8

32

42

M328

C114

H199

I257

I261

U390

U395

1-Chlorobutane

H199

Chlorocyclohexane

C114

Chlorocyclopropane

C90

H199

Chloroethane

C114

H199

Chloroethylene

C114

H199

Chloroform

C114

C160

H199

H243

I310

I312

M373

U401

H240

M373

U405 Chloroform-d

C157


Index Terms

Links

Chloromethane

C114

H199

Chloropropanes

C114

H199

Chloropyridines

C114

Chlorotrimethylsilane

H228

Chlorotriphenylsilane

H228

Cholesterol

C156

Chromone

H195

Chrysene

U398

Cinnoline

C110

Citric acid

U403

H196

M327

M321

Condensed – alicyclics

C94

– aromatics

46

52

– heteroaromatic rings

C109

H193

Conjugated alkenes

U387

– dienes

C85

H174

– common

C160

H243

Coronene

U399

Coumarin

H195

Contaminants

Coupling – H–C–N–H

H223

– with hydroxy protons

H202

– with SH protons

H214

Crotonaldehyde

I287

U393

Crotonic acid

I292

U394

– esters

I294

18-Crown-6 Cubane

M376

M379

C94

Cyanates

H213

– aliphatic

M345

I277


Index Terms

Links

Cyanates (Cont.) – aromatic Cyanides

M345 4

35

37

39

C126

H212

I246

I275

I276

M318

U386

– aliphatic

M343

– aromatic

M344

α-Cyano-4-hydroxycinnamic acid

M381

M382

32

37

40

42

49

C90

H176

I247

I253

M318

– alkenes

32

33

50

I253

– amines

C123

H209

M340

34

36

C119

H204

32

35

C135

C136

H219

H220

M359

C129

H215

M351

32

37

40

42

49

C90

H176

I247

I253

M318

Cycloalkanols

32

37

M331

Cycloalkanones

32

35

41

42

C135

C136

H219

H220

Cyclic – alkanes

– ethers

M335 – ketones – sulfides Cycloalkanes

M359 Cycloalkenes

32

33

50

I253

Cyclobutanes

C90

C95

H176

I254

H219

I288

1,2-Cyclobutanedione

H220

Cyclobutanol

H203

Cyclobutanone

C136


Index Terms

Links

Cyclobutenes

C93

Cycloheptane

C90

H176

I248

I254

Cycloheptanone

C136

I288

Cycloheptatriene

C93

H177

Cycloheptene

C93

H177

Cyclohexadienes

C93

H177

M319

Cyclohexane

C95

C160

H176

H243

M372

U405

H179

I245

Cyclohexanecarboxaldehyde

C133

Cyclohexane-d12

C158

Cyclohexanecarbonyl chloride

C142

Cyclohexanecarboxylate ion

C137

Cyclohexanecarboxylic acid

C137

1,3-Cyclohexanedione

H220

Cyclohexanes

41

H241

C92

I254 Cyclohexanethiol

C128

H214

Cyclohexanol

C118

H203

I264

Cyclohexanone

C136

H219

I288

Cyclohexanones

M360

Cyclohexanonitrile

C126

Cyclohexene 2-Cyclohexene-l-one Cyclohexenes N-Cyclohexyl acetamide

C93

H176

C136

I289

35

39

40

I248

I254

M319

50

C141

Cyclohexyl – acetate

C138

– methyl ether

C119

– methyl ketone

C135

Cyclohexylamine

C122

H208


Index Terms

Links

Cyclohexyldimethylamine

C122

Cyclohexyldimethylphosphine

C145

Cyclohexylmethylamine

H209

1,3-Cyclooctadiene

C177

1,5-Cyclooctadiene

C93

Cyclooctatetraene

C93

Cyclooctene

C93

H177

Cyclopentadiene

C93

H176

Cyclopentane

C95

H176

Cyclopentanes

C91

I254

C136

H219

I288

40

C93

H176

7

49

C90

C95

H176

H178

I245

I250

I251

I254

M318

C90

H203

Cyclopentanone Cyclopentenes 2-Cyclopenten-l-one Cyclopropanes

Cyclopropanol Cyclopropanone Cyclopropenes Cyclopropenone

C136

H219 C93

H176

I248

I254

C136

Cyclopropyl methyl ketone

C90

C135

Cyclopropylamine

C90

H208

Cylohexylmethylamine

C122

Cysteine

C149

Cystine

C149

Cytidine

C154

H238

Cytosine

C154

H237

H234

U404

D Decalins 2'-Deoxyadenosine

C94 C155

H239


Index Terms

Links

2'-Deoxyguanosine

C155

Diacetamide

C143

Diacetyl

C135

N,N-Diacetylmethylamine

C143

Diazen-N-oxides

H210

Diazen-N-sulfides

I274

Diazo compounds

35

Diazophenyl derivatives

43

Dibenz[a,h]anthracene

U399

Dibenzo-l,4-dioxin

C110

Dibenzofuran

C110

Dibenzothiophene

C110

Dibenzoylamine

M367

Dibromoacetic acid

C115

1,1-Dibromoacetone

C135

Dibromoethanes

C115

1,1-Dibromoethylene

C115

cis-1,2-Dibromoethylene

C115

trans-l,2-Dibromoethylene

C115

H239 H220 I274 I276

M342

U386

H197

H200

Dibutyl – carbonate

C143

– phthalate

M373

– sulfide

C128

– sulfone

M354

H227

Di-tert-butyl – ketone

C134

– hydrazone

C125

– sulfide

C128

– sulfone

H216

– thioketone

C132

Di-tert-butyldiazene-1 -oxide

H211


Index Terms

Links

Dichloroacetate ion

C137

Dichloroacetic acid

C114

1,1-Dichloroacetone

C135

Dichlorodimethylsilane

H228

Dichloroethanes

C114

1,1 -Dichloroethylene

C114

cis-1,2-Dichloroethylene

C114

Dichloromethane

C114

α,α-Dichlorotoluene

C114

Dicyclohexyl carbodiimide

C125

C137

H199

H199

U405

32

33

41

H174

U387

U393

– aliphatic

C85

H174

– conjugated

C85

H174

Dienes

Diesters

43

– unsaturated

43

Diethanolamine

45

C122

Diethyl – disulfide

C130

– ether

C160

H204

M372

U405

– ethylphosphonate

C145

– ketone

C134

– sulfate

C131

– sulfide

C128

– sulfite

C131

H243

I266

H217

N,N-Diethyl – acetamide

C141

– butyramide

C141

– formamide

C140

Diethylamine

C121

H208


Index Terms

Links

1,3-Diethylurea

H227

Diethylnitrosamine

C124

Difluoroacetic acid

C112

1,1-Difluoroethane

H198

Difluoromethane

C112

Diglyme

C160

H243

Dihydrazides

I296

9,10-Dihydroanthracene

C96

H181

C119

H205

C96

H181

Dihydrofurans 9,10-Dihydrophenanthrene 3,4-Dihydro-2H-pyran

C119

2,3-Dihydrothiophene

H215

2,5-Dihydrothiophene

C129

H215

2,6-Dihydroxyacetophenone

M381

M382

2,5-Dihydroxybenzoic acid

M381

M382

1,1-Diiodoethane

H201

1,2-Diiodoethane

C116

cis-l,2-Diiodoethylene

C116

trans-1,2-Diiodoethylene

C116

Diiodomethane

C116

H201

H201

Diisopropyl – carbodiimide

C125

– ketone

C134

– sulfide

C128

Diisopropylamine

H208

Diisopropylnitrosamine

C124

H210

12

14

Diketones

I287

15

C135

I288 Dimedone

C118

Dimethoxymethane

C120

2,2-Dimethoxypropane

C120

H206


Index Terms N,N-Dimethyl acetamide

Links C141

H225

Dimethyl – acetylenedicarboxylate

C139

– butylphosphonite

C145

– carbonate

C143

H227

C81

C119

– ether – ethylphosphonate

H231

– fumarate

C139

– glycol

M372

– maleate

C139

– malonate

C139

– methylphosphonate

H231

– oxalate

C139

– phenylphosphonate

H231

– succinate

C139

– sulfate

C131

H217

– sulfide

C128

H215

– sulfite

H217

– sulfone

C130

H216

– sulfoxide

C130

C160

– sulfoxide-d6

C158

H241

– trithiocarbonate

C143

H204

H216

H243

C160

H224

N,N-Dimethyl – formamide

C81

C140

H243 – sulfinamide

H217

– thioacetamide

C132

Dimethylamine

C121

N,N-Dimethylaniline

C122

Dimethylazine

H212

3,3-Dimethyl-2-butanone

C134

H208


Index Terms

Links

4,4-Dimethyl-2,5-cyclohexadien-1-one

C136

5,5-Dimethyl-1,3-cyclohexanedione

C118

N,N’-Dimethylethylenediamine

C122

NN-Dimethylformamide

I297

1,3-Dimethyl-2-imidazolidinone

C143

Dimethylnitrosamine

C124

2,4-Dimethyl-3-pentanone

C134

Dimethylphosphine

H229

Dimethylphosphine sulfide

H230

2,2-Dimethyl-l-propanethiol

C128

2,2-Dimethyl-1 -propanol

C117

Dimethylsilane

H228

Dimethylsilanol

H229

1,3-Dimethylurea

H227

Dimethylvinylphosphine sulfide

H230

Dineopentyl sulfide

C128

N,N-Dinitromethylamine

C124

Dioctyl phthalate

M373

Diols

M371 H210

42

1,3-Dioxane

H206

I265

1,4-Dioxane

C119

C160

H205

I265

M372

U405

1,3,2-Dioxathiane oxide

C131

1,3,2-Dioxathiolane dioxide

H217

1,3-Dioxolane

C120

H206

– disulfide

C130

H216

– ether

C119

H206

– methylphosphonate

C146

– sulfide

C129

– sulfone

COO

H243

Diphenyl U395

H215


Index Terms

Links

Diphenyl (Cont.) – sulfoxide

M353

Diphenylamine

C123

Diphenylsilanol

H229

Diphenylvinylphosphine oxide

H229

Diphenylvinylphosphine sulfide

H230

N,N-Dipropyl acetamide

C141

Dipropyl sulfide

C128

Dipropylamine

C121

Dipropylnitrosamine

C124

U396

H208

Disulfide – dimethyl

U403

Disulfides

40

45

C74

C75

C98

C130

H161

H162

H183

H216

I280

M351

U386 1,2-Dithiane

H216

1,3-Dithiane

C129

1,4-Dithiane

C129

1,3-Dithietane

C129

Dithioacids

I283

Dithiocarbonates

I285

M302

Dithiocarboxylic acid esters

C132

M357

Dithioerythritol

M376

1,3-Dithiolane

C129

Dithiophosphate – trimethyl

C146

Dithiothreitol

M376

Dithranol

M381

M383

Divinyl – ether

I266


Index Terms

Links

Divinyl (Cont.) – ketone

H219

DMSO

C130

DSS

C159

I289 H216 H242

E Elements – isotope patterns Enamines

23 I251

End absorption

U405

Enol esters

M363

Enols

C118

H204

I263

7

34

45

C119

H204

I245

I250

I254

I265

I266

Epoxides

– aliphatic Esters

M336 3

4

6

7

8

9

12

14

15

32

33

40

42

43

66

C138

H221

I292

U386

– of aromatic acids

65

M363

– ethyl

35

38

42

– methyl

36

41

C138

– phenol

42

I293

– propyl

37

39

– saturated

M361

– unsaturated

M362


65

– vinyl

I293

Ethane

C71

I293

U388 C81

H161


Index Terms

Links

1,2-Ethanedithiol

C128

Ethanesulfonyl chloride

C131

Ethanethiol

C128

H214

U402

Ethanol

C117

C160

H202

H243

M371

U405

Ethanolamine Ethers

C122 3

4

8

9

32

33

40

41

42

45

57

C119

H204

I245

I263

I264

U386 – acetylene – aliphatic – alkenylsubstituted

M334 32

M333

I251

– alkyl aryl

M337

– alkyl cycloalkyl

M335

– allyl

M334

– aromatic

C119

H206

M337

34

36

C119

H204

H221

H243

– cyclic

M335 – ethyl

38

– methyl

36

– phenol

42

– propyl

39

I245

– unsaturated

M334

– vinyl

M334

N-Ethyl acetamide

C140

H224

C138

C160

M372

U405

Ethyl – acetate – acrylate

H222


Index Terms

Links

Ethyl (Cont.) – benzoate

H222

– cyanate

H213

– disulfides

H216

– group

C74

H162

– isocyanate

H213

I278

– isocyanide

C126

H213

– isothiocyanate

H213

– methyl ether

C119

– methyl ketone

C134

– methyl sulfide

H215

– methyl sulfone

C130

H216

– N-methylcarbamate

C143

H227

– nitrite

H232

– phenyl ketone

H219

– thiocyanate

C127

– trifluoroacetate

H222

– vinyl ether

H204

– vinyl sulfide

C129

N-Ethyl formamide

C140

Ethylamine

C121

Ethylbenzene

H181

Ethylene

H219

H213

H208

C86

C87

– carbonate

C143

H227

– glycol

C117

M371

– – dimethyl ether

C119

– oxide

I266

– sulfide

C129

– trithiocarbonate

H227

Ethylenes, monosubstituted

H170

N-Ethylidene-tert-butylamine

C124

H168

H215


Index Terms

Links

Ethylidene triphenyl phosphorane

C147

Ethylmethylamine

C122

Ethylthioethyne

C129

Ethyltriacetylsilane

C144

Ethylurea

H227

Ethynyl methyl ketone

C135

F Fast atom bombardment (FAB) mass spectra Fatty acid derivatives Fermi resonance

M374 42 I245

I252

M381

M383

Fluorene

C96

H181

M321

Fluorides

10

29

35

36

38

43

54

C112

H198

I260

M373

10

29

35

36

38

43

54

C112

H198

I260

M373

Ferulic acid

– aliphatic

M328

– aromatic

M329

Fluoro compounds

– aliphatic

M328

– aromatic

M329

Fluoroacetic acid

C112

Fluoroacetone

C134

Fluoroacetylene

H198

Fluoroalkanes

M328

Fluorobenzene

C113

Fluorocyclohexane

C113

Fluorocyclopropane

H198

I279

I286

H198


Index Terms

Links

Fluoroethane

C112

H198

Fluoroethylene

C112

H198

Fluoromethane

C112

H198

1-Fluorooctane

C112

Fluoropropanes

C112

Fluoropyridines

C113

Formaldehyde

C133

H218

Formamides

C140

H224

I297

Formanilides

M365

Formate ion

C137 I291

I293

M362

C137

H220

I291

Formates Formic acid – esters

9

Formic anhydride

C142

Fructose

C153

Fullerene

C96

Fulvene

C93

H176

I254

C104

C111

H186

M371

35

41

H188

I258

I259

M323

C107

C144

Furan

H237

U400 5H-Furan-2-one Furans Furazan

H223

H186

Furyl ketones

40

42

H166

H168

C99

C106

G Geminal Coupling Germanium compounds

H232 Glucose

C152

H236

Glutamic acid

C150

H234


Index Terms

Links

Glycerol

C117

M379

Glycine

C148

H233

Glycol ethers

32

33

42

Glycols

32

33

39

41

C117 – ethylene

39

– vicinal

M331

Group IV elements

C144

Guanidines

M303

Guanidinium ion

U386

Guanine

C154

U404

Guanosine

C155

H238

H 1

H NMR Spectroscopy

Halides

H161 3

4

8

9

26

54

C112

H198

I260

M328

– aliphatic

M328

– aromatic

M329

Haloboroxines Halogen compounds

I308 3

4

8

9

26

54

C112

H198

I260

M328

– aliphatic

M328

– aromatic

M329

Halogenides

3

4

8

9

26

54

C112

H198

I260

M328

– aliphatic

M328

– aromatic

M329


Index Terms Heptane Heteroaromatic compounds Heteroatom indicators

Links C71

U405

9

53

I258

M323

H186

H243

M372

29

Hexabromoethane

C115

Hexachloroacetone

C135

Hexachloroethane

C114

Hexadecylpyridinium bromide

M377

Hexafluoroethane

C112

Hexane

C104

C71

I289 M380 C160

U405 1-Hexanethiol

C128

2,5-Hexanedione

C135

Hexanols

C117

2-Hexanone

C134

Histidine

C151

Homoallylic couplings

H169

Homologous mass series

32

Hydrazides

36

Hydrazines

H182

Hydrazones

C125

Hydrochlorides

I309

Hydrogen bonds

H202

Hydroperoxides

I267

– aliphatic Hydroxylamines

I296 H211

M332 34

4-Hydroxyproline

C151

N-Hydroxypyridinium chloride

C104

Hyrdrogen bonds

H235

H235

9


Index Terms

Links

I Imidazole

41

C104

C111

H186

H227

Imidazolium – anion

C104

– cation

C104

Imidazolo[l,2-a]pyridine

H195

Imides

H186

11

12

C143

I296

M367

U386

– cyclic

12

M367

Imines

4

C124

H211

Indane

C94

C96

H181

I272

1-Indanone

H220

Indazole

C109

H194

C94

C96

H181

C109

H193

M326

Indene Indium, trimethyl Indoles

C146 43 U401

Indolizine Iodides

C109

H194

30

43

46

54

C116

H201

I262

U385

30

43

46

54

C116

H201

I262

U385

H201

U395

– aliphatic

M328

– aromatic

M329

lodo compounds – aliphatic

M328

– aromatic

M329

Iodoacetylene

H201

Iodoalkanes

M328

Iodobenzene

C116

Iodobenzenes

I261


Index Terms

Links

1-Iodobutane

H201

Iodocyclohexane

C116

H201

Iodocyclopropane

C90

H201

Iodoethane

C116

H201

Iodoethylene

C116

H201

Iodomethane

C116

H201

Iodopropanes

C116

H201

Iodopyridines

C116

IR Spectroscopy

I245

Isobutane

H161

Isobutenes

H173

Isobutyraldehyde

C133

Isobutyric acid

C137

Isobutyronitrile

H218

I287

C126

H212

I276

Isocyanates

C127

H213

I277

– aliphatic

M345

– aromatic

M346

Isocyanides

C126

H212

I275

– aliphatic

M344

– aromatic

M344

Isocyanurates

I296

Isoleucine

C149

H233

Isonitriles

C126

H212

– aliphatic

M344

– aromatic

M344

Isopropanol

C117

H203

– acetate

C138

H221

– benzoate

H222

I275

Isopropyl

– group

C75

– isocyanate

H163

H213


Index Terms

Links

Isopropyl (Cont.) – methyl ketone

C134

– methyl sulfone

C130

– phenyl ketone

H219

H219

N-Isopropyl – acetamide

C141

H225

– formamide

H224

Isopropylamine

C121

Isopropylbenzene

H181

Isopropyldimethylamine

C122

Isoquinoline

C110

Isoquinoline N-oxide

H196

Isoquinolines

M326

Isothiazole

C104

H186

Isothiocyanates

C127

H213

H208

H196

U401

I278

M347

C120

H206

U386 Isotope patterns – for combinations of C1, Br, S, and Si

26

– calculation of

24

28

Isotopes – abundance of

16

– patterns for elements

23

Isoxazole

C104

22 H186

K Karplus equation Ketals

H167 4

37

I264

I265

– ethylene

39

43

– thioethylene

44

Ketenes

I289

U386


Index Terms

Links

Ketimines

C124

Ketoesters

I293

Keto-enol tautomerism Ketones

I273

I274

3

4

7

8

12

14

15

32

33

34

35

37

40

42

43

45

64

C134

H219

I287

M359

– α,(β-unsaturated

U388

– aliphatic

H220

– alkyl phenyl

U392

– aromatic

M360

– cyclic

M359

32

35

41

42

C135

C136

H219

H220

9

C125

H211

12

14

35

68

C140

C141

H223

H225

I295

I296

M365

11

12

32

33

34

35

36

38

40

66

C139

H223

M359 – ethyl

39

– halogeneted

C134

– long-range couplings

H220

– methyl – unsaturated Ketoximes

I246 M359 4 I274

L Lactams

Lactic acid Lactones

I292


Index Terms

Links

Lactones (Cont.)

I292

M364

Lead compounds

C99

C105

C106

C107

C144

H171

H183

H232

Leucine

C148

H233

Lithium tetramethylborate

C147

Long-range couplings

H167

H178

H180

H169

H220 Lysine

C150

H234

M Magic bullet

M376

Maleic anhydride

C142

Maleinimide

C143

Malonic acid

C137

Malonitrile

C126

Mass spectrometry

M313

H226

I299

H221

I292

Matrix-assisted laser desorption ionization (MALDI) mass spectra

M380

McLafferty rearrangement

M315

M317

M323

M325

M331

M332

M338

M339

M343

M344

M353

M355

M358

M359

M360

M361

M362

M364

3

7

8

10

32

33

41

45

62

C128

H214

I280

Mercaptans

U386 – aliphatic

M349

– aromatic

M349

2-Mercaptoethanol

C128


Index Terms Mercury compounds Methacrylonitrile Methane

Links C99

C146

H183

M323

H171

H178

H202

H243

M318 C71

H161

Methanesulfonic acid

C131

– ester

H217

Methanesulfonyl chloride

C131

H217

Methanethiol

C128

H214

Methanol

C117

C160

M371

U405

Methanol-d1

C158

H241

Methanol-d4 C158

H241

Methionine

C149

N-Methyl acetamide

C140

H224

– acetate

C138

H221

– acrylate

C139

H222

– benzenesulfonate

C131

– benzoate

C139

H222

– butyrate

C138

H222

– chloroacetate

C139

– cyclohexanecarboxylate

C138

– dichloroacetate

C139

– disulfides

H216

– dithioacetate

C132

– esters

C138

– formate

C138

H221

C72

C74

– isobutyrate

C138

H222

– isocyanate

C127

H213

– isocyanide

H213

Methyl

– group

H162 I278


Index Terms

Links

Methyl (Cont.) – isopropyl ether

C119

– isothiocyanate

C127

– methanethiolsulfinate

C131

– methanethiolsulfonate

C131

– nitrate

H232

– perchlorate

H232

– phenyl sulfone

H216

– phenyl sulfoxide

H213

I279

C130

H216

M352

– pivalate

C138

H222

– propiolate

C139

– propionate

C138

– propyl ether

C119

– propyl ketone

C134

– dimethylhydrazone

C125

– propyl sulfone

COO

– thiocyanate

H213

– trichloroacetate

C139

– valerate

C138

H222

– vinyl ether

C119

H204

– vinyl ketone

C135

H219

– vinyl sulfide

H215

– vinyl sulfone

H216

– vinyl sulfoxide

H216

H222 H219

N-Methyl – γ-butyrolactam

H225

– formamide

C140

– phthalimide

C143

– β-propiolactam

H225

– succinimide

C143

– δ-valerolactam

H225

H224

I297


Index Terms

Links

S-Methyl thioacetate

C132

Methyl-tert-butylamine

C122

Methylamine

C121

H208

N-Methylaniline

C122

H209

N-Methylazetidine

C123

Methylazine

H212

N-Methylaziridine

C123

1-Methylbenzotriazole

C109

2-Methylbutane

C71

3-Methyl-2-butanone

C134

3-Methyl-l-butyne

H175

Methylcyclopropane

I270

C95

Methylene – chloride

M372

– fluoride

H198

Methylenecyclopentadiene

C93

Methylenedioxy group

I245

Methylisopropylamine

C122

Methyllithium

C147

4-Methylmorpholine

H209

2-Methyl-2-nitropropane

C123

Methyloxirane

H204

Methylphenyldiazene

H211

Methylphosphine

H229

1-Methylpiperazine

H209

1-Methylpiperidine

C123

2-Methylpropane

H232 H210

H209

C71

2-Methyl-2-propanesulfonic acid

C131

– chloride

C131

2-Methyl-2-propanethiol

C128

2-Methyl-2-propyl isocyanide

H213


Index Terms

Links

Methylpropylamine

C122

N-Methylpyridinium iodide

C104

N-Methylpyrrolidine

C123

Methylsilane

H228

N-Methyl-N-silylaminosilane

H228

Mineral oil Molecular weight, determination of

I311 31

Monosaccharides

C152

H236

Monosubstituted naphthalenes

H184

H185

Morpholine

C119

C123

H205

H209

44

C96

H180

N Naphthacene

U398

Naphthalenes

43 U398

– monosubstituted

C100

C101

1,4-Naphthoquinone

C136

I290

Naphthoquinones Neopentane 14

1

N- H coupling

43 C71 H212

H223

C124

I271

Nitrates

C78

I271

U386

Nitric acid esters

C78

I271

U386

4

35

37

39

C126

H212

I246

I275

M318

U386

Nitramines

Nitriles

– aliphatic

M343

– aromatic

M344

Nitro compounds

3

4

8

10

34

36

38

60

C123

H210

I270

U386


Index Terms

Links

Nitro compounds (Cont.) – aliphatic

M341

– aromatic

M342

Nitrobenzene

C124

H210

3-Nitrobenzyl alcohol

M375

M379

1-Nitrobutane

C123

H210

2-Nitrobutane

C123

Nitrocyclohexane

C124

Nitrocyclopentane

H210

N-Nitrodimethylamine

C124

Nitroethane

C123

Nitroethylene

H210

Nitrogen compounds Nitromethane

C121

H207

H210

U402

46

C123

I272

U396

H210

29

59

I268

M339

3

C123

C124

1-Nitrooctane

C123

2-Nitrophenol

H203

2-Nitrophenyl octyl ether

M376

M380

Nitropropanes

C123

H210

Nitrosamines

C124

H210

10

36

H210

U386

Nitrosobenzene

C124

H210

Norbornadiene

C94

Norbornane

C94

Norbornene

C94

Norcamphor

H177

Nucleotides

U403

– and nucleosides

C154

Nujol

U390

H210

N-Nitromethylamine

Nitroso compounds

I272

H237

I311


Index Terms

Links

O Octane

C71

n-Octanes

C76

Olefins

4

7

8

10

32

37

40

41

42

45

50

C82

H168

I246

I248

M315

33

50

I253

U385 – branched – cyclic

M315 32

– unbranched

M315

Organometallics

C147

Ornithine

C150

Ortho esters

9

H232 C120

Ovalene

U399

Oxalic acid

C137

1,3-Oxathiane

C129

1,4-Oxathiane

C129

H215

Oxazole

C104

H186

Oxetane

C119

H205

N-Oxides Oximes

4

9

I272

U386

I273

– aromatic

I273

Ozonides

I292

34

– aliphatic Oxiranes

H206

C125

H211

7

34

45

C119

H204

I245

I250

I254

I265

I266

I267


Index Terms

Links

P 1,3-Pentadiene

H174

Penta(isopropyloxy) phosphorane

C147

Pentaerythritol

C117

Pentane

C71

M371

U405

2,4-Pentanedione

C118

C135

H220

1-Pentanethiol

C128

1-Pentanol

C117

Pentanones

C134

3-Penten-l-yne

H175

2-Pentyne

H175

H180

U398

H203

I264

U390

42

56

Peracids

I267

Perchlorate – methyl

H232

Perfluoralkanes

C113

Perfluoroalkyl derivatives

44

Peroxides

I267

– aliphatic

M337

– cyclic

36

Perylene Phenanthrene

U399 C96

Phenazine

C110

Phenol

C118 U395

– derivatives

42

– esters

42

– ethers

42

Phenolate Phenols

U390

U395

9

33

I263

M332


Index Terms

Links

Phenothiazine

C110

Phenoxathiin

C110

Phenoxazine

C110

H197

– acetate

C138

H222

– isothiocyanate

H213

I279

– propyl ketone

H219

Phenyl I294

N-Phenyl – acetamide

C141

– formamides

H224

– methanesulfonamide

H217

Phenylacetylene

H175

Phenylalanine

C150

Phenylphosphonic acid

C146

Phosphanes

10

Phosphates

10

– alkyl

43

– alkyl esters – ethyl

H225

I297

H234

I306

M369 35

Phosphine

H229

Phosphine oxides

H229

Phosphine sulfides

H229

Phosphines

C145

M369 H229

I305

H231

I306

M369

Phosphinic acid – anhydrides

I307

– esters

I306

Phosphonic acid – derivatives – esters

C145 I306

Phosphonium compounds

C145

Phosphonous acid derivatives

H230

H229


Index Terms Phosphoranes

Links C147

Phosphoric acid – anhydrides

I307

– derivatives

C145

– esters

H231

I306

Phosphorus compounds

10

30

H229

I246

I283

I305

– aliphatic

C145

H229

– aromatic

C146

Phosphorus ylids

H231

43 C145

35

38

M369

M370

I312

M363

M373

H197

M327

H226

I299

Phthalate – esters

44

– diethyl

I294

Phthalazine

C110

Phthalic acid

I292

– anhydride

C142

Phthalimide

I298

Piperazines

C123

M341

Piperidines

41

C123

– N-alkylsubstituted

42

H209

2-Piperidone

M365

M366

Pivalaldehyde

C133

H218

Pivalate ion

C137

Pivalic acid

C137

H221

I291

32

33

37

C94

M319

45

M316

U387

M374

M375

M377

Polycyclic alkanes Polyenes Polyethylene glycol Polyethers Polyhaloalkanes

M361

41

58 M329


Index Terms Polyols

Links C117

Polypeptides Polyynes Potassium bromide

I291

I296

M316 I311

Progesterone

C156

Proline

C151

H235

Propane

C71

C81

1,3-Propane sultone

H217

Propanediols

C117

1,3-Propanedithiol

H214

Propanesulfonic acids

C131

Propanesulfonyl chlorides

C131

Propanethiols

C128

H214

1-Propanol

C117

H202

2-Propanol

C117

U405

Propargyl alcohol

C118

Propioisonitrile

C126

H213

β-Propiolactone

C139

H223

Propiolaldehyde

C133

Propiolic acid

C137

Propionaldehyde

C133

Propionate ion

C137

Propionates

H161

I293

H218

I293

Propionic acid

C137

– anhydride

C142

Propionitrile

C126

Propionyl chloride

C142

H220 H212

Propyl – acetate

H221

– group

C74

– isocyanate

H162

H213


Index Terms N-Propyl acetamide

Links C141

H224

2-Propyl – isocyanide

H213

– isothiocyanate

H213

– thiocyanate

H213

Propylamine

C121

H208

C87

H168

Propylene Propylene carbonate

C143

N-Propylidene isopropylamine

C124

Propyne

C89

H175

Protonation of amines

C121

Purine

C109

H194

4H-Pyran

C119

H205

2H-Pyran-2-one

C139

H223

Pyrans

41

2H-Pyran-2-thione

H217

Pyrazine

C104

– N-oxide

H187

Pyrazoles

41

H187

M323

M326

C104

C111

H186

Pyrazolium – anion

C104

– cation

C104

Pyrazolo[l,5-a]pyridine

H194

Pyrene

C96

U399

Pyridazine

C104

H187

– N-oxides

H187

M325

Pyridazines

M325

Pyridine

C104

C111

C160

H187

H243

M372

U400

U405

– N-oxide

C104

H187

M325

Pyridine-d5

C158

H241

U400


Index Terms Pyridines – alkylsubstituted

Links 4

41

43

C108

H191

M324

42

Pyridinium ion

C104

2-Pyridone

M365

Pyridone derivatives

C105

H187

42

Pyrimidine

C104

Pyrones

H205

Pyrrole

C104

H187

M325

U400

C111

H186

M318

H189

I258

I259

U400 Pyrroles

41 M324

Pyrrolidine Pyrrolidines

C123 40

2-Pyrrolidone

M366

Pyrryl ketones

42

Pyruvic acid

H209

I292

Q Quadrupole relaxation

H207

Quinazoline

C110

H196

M327

Quinoline

C110

H195

U401

– N-oxide

H196

M325

Quinolines

43

44

M326

Quinones

14

35

C136

I289

I290

U397

C110

H196

M327

Retro-Diels–Alder reaction

M319

M360

Ribose

C152

Quinone oximes Quinoxaline

I288

I273

R


Index Terms

Links

S Salicylaldehyde

I287

Salicylic acid

I292

– derivatives

43

Selenium compounds

C99

Selenacyclopentadiene

C104

H186

Serine

C149

H233

SH chemical shifts

H214

Silane

H228

Silanes

10

40

H228

I246

10

26

37

40

41

C73

C83

C99

C100

C101

C105

C106

C107

H171

H183

H228

I304

M369

H243

I310

I304 Silanols

H228

Silicon compounds

Siloxanes

I304

Silyl ethers

M369

Sinapinic acid

M382

M383

Sodium – propionate

H220

– tetraphenylborate

H232

Solvents

C157

H240

M371

U405

D-Sorbitol Spin quantum number

C117 2

Spiro[4,5]decane

C94

Spiro[5,5]undecane

C94


Index Terms

Links

Steroids

C156

trans-Stilbene

U394

Styrene

I251

I257

U390

Succinic acid

C137

H221

I292

– anhydride

C142

H226

I299

Succinimide

C143

H227

I297

U403

Succinonitrile

C126

Sulfates

C131

Sulfides

3

7

8

9

32

33

36

41

45

62

C128

H215

I280

U386

– aliphatic

M350

– aromatic

M351

– cyclic

C129

– ethyl

39

– methyl

38

– vinyl

H215

U394

M351

I246

M350

Sulfinates

I281

Sulfinic acid esters

I281

Sulfinic acids

C131

H217

Sulfolane

C130

M377

3-Sulfolene

H216

Sulfonamides

I281

I282

– aromatic

M356

Sulfonates

38

– ethyl

38

Sulfones

40

I282

34

38

40

H216

I281

I282

– aliphatic

M353

– aryl

M354

C130

M355


Index Terms

Links

Sulfones (Cont.) – cyclic

M354

– ethyl

38

Sulfonic acid esters

I282

M355

M356

Sulfonic acids

C131

H217

M355

Sulfonium salts

C130

H216

34

38

C130

H216

26

29

36

38

39

41

I273

I274

I278

I302

M323

M346

M347

U386

Sulfuric acid derivatives

C131

H217

Sulfurous acid derivatives

C131

H217

Sulfoxides

I281 – aliphatic

M352

– aryl

M352

Sulfur compounds

Suspension media IR

I311

T Telluracyclopentadiene Terephthalic acid

C104 I292

Tertiary alkylamides

H224

Testosterone

C156

Tetrabromoethylene

C115

Tetrabutylammonium ion

H208

Tetrabutylphosphonium iodide

C145

Tetrachloroethylene

C114

Tetraethylammonium ion

C121

H208

Tetraethylphosphonium iodide

C145

H229

Tetrahydrofuran-d8

C158

H241


Index Terms Tetrahydrofurans 1,2,3,4-Tetrahydronaphthalene Tetrahydropyran

Links 40

C119

C160

H205

H243

I265

M371

U405

C94

C96

H181

42

C119

H205

43

44

Tetrahydrothiapyrane

M351

Tetrahydrothiophene

M351

1,1,2,3-Tetrahydroxypropane

C117

Tetralins

40

α-Tetralone

H220

Tetramethyl orthocarbonate

C120

H206

Tetramethylammonium ion

C121

H208

N,N,N',N′-Tetramethylethylenediamine

C122

Tetramethylgermane

C144

Tetramethyllead

C144

2,2,4,4-Tetramethyl-3-pentanone

C134

Tetramethylphosphonium iodide

C145

Tetramethylsilane

C144

N,N,N',N′-Tetramethylthiourea

C143

Tetramethyltin

C144

N,N,N',N'-Tetramethylurea

C143

Tetraphenylarsonium chloride

C147

Tetraphenylgermane

C144

Tetraphenyllead

C144

Tetraphenylsilane

C144

Tetraphenyltin

C144

Tetrapropylammonium ion

C121

Tetravinylsilane

C144

1,2,4,5-Tetrazine

C104

Tetrazole

C104

1,2,3-Thiadiazole

C104

1,2,5-Thiadiazole

H186

H232

H228

M372


Index Terms

Links

Thiairane

C129

H215

Thiane

C129

H215

Thiazole

C104

H186

Thiethane

C129

H215

Thioacetals

8

Thioacetamide

C132

U403

Thioacetic acid

C132

H217

Thioacid – chlorides

I283

– fluorides

I283

Thioamides

4

C78

C132

Thioanisole

C129

H215

Thiobenzamide

C132

Thiocarbamides

4

C132

I283

Thiocarbonates

I284

I285

I302

Thiocarbonic acid derivatives

I283

I283

Thiocarbonyl – compounds

U386

– derivatives

I283

– groups

C132

Thiocarboxylate derivatives

H217

Thiocarboxylic acid O-esters

4

Thiocarboxylic acid S-esters

C132

H217

M357

4

C132

H217

H213

I278

Thiocarboxylic acids Thiocyanate

I279

Thiocyanate – anion

C127

– inorganic

U402

Thiocyanates

C127

– aliphatic

M346

– aromatic

M347


Index Terms

Links

Thioesters

C132

H217

I283

M357

Thioethers

3

7

8

9

32

33

36

41

45

62

C128

H215

I280

U386

– aliphatic

M350

– aromatic

M351

– cyclic

C129

– ethyl

39

– methyl

38

– vinyl

H215

M351

I246

M350

Thioethylene ketals

44

Thioglycerol

M376

M379

Thioketones

4

C132

Thiolactams

I283

I283

Thiolane

C129

H215

– oxide

C130

H216

3

7

8

10

32

33

41

45

62

C128

H214

I280

H190

Thiols

U386 – aliphatic

M349

– aromatic

M349

Thiophenes

C104

C111

H186

I259

M323

U400

– alkylsubstituted

42

Thiophenol

U396

5H-Thiophen-2-one

H217

Thiophenoyl derivatives

43

2H-Thiopyran

H215

4H-Thiopyran

H215


Index Terms Thiosulfonic acid ester

Links I282

Thioureas

C142

I284

1,4-Thioxane

C119

H205

Threonine

C149

H233

Thymidine

C154

H238

Thymine

C154

H237

C78

Tin compounds Toluene

I285

I303

C99

C105

C106

C107

C144

H171

C103

C160

H180

H243

I257

M372

U390

U394

U400

U405 p-Toluenesulfonates

M356

1,2,4-Triazine

H187

1,3,5-Triazine

C104

H187

1,2,3-Triazole

C104

C111

1,2,4-Triazole

C104

C111

1,2,5-Triazole

H186

1,3,4-Triazole

C104

1,1,1-Tribromoacetone

C135

1,1,1-Tribromoethane

C115

Tribromoethylene

C115

H186

Tributyl – phosphate

C145

– phosphite

C145

Tributylphosphine

C145

– oxide

C145

– sulfide

C146

Trichloroacetaldehyde

C133

Trichloroacetate ion

C137

Trichloroacetic acid

C114

1,1,1-Trichloroacetone

C135

I287 C137


Index Terms

Links

1,1,1-Trichloroethane

C114

2,2,2-Trichloroethanol

C118

Trichloroethylene

C114

Trichloromethylsilane

H228

Trichloropropylsilane

C144

α,α,α-Trichlorotoluene

C114

H199

Triethanolamine

C122

M377

Triethoxyphosphine sulfide

H231

H203

Triethyl – orthoformate

C120

– phosphate

C145

– phosphite

H230

Triethylamine

C121

Triethylphosphine

H229

– oxide

H229

– sulfide

H230

Trifluoroacetates

H206

H208

U402

I296

Trifluoroacetic acid

C112

C137

1,1,1-Trifluoroacetone

C134

Trifluoromethane

C112

2,2,2-Trifluoroethanol

C118

Trifluoromethyl group

38

40

α,α,α-Trifluorotoluene

C113

H198

Trihydroxymethane

C117

Triiodomethane

C116

H198 M329

H201

Trimethyl – borate

H232

– orthoformate

C120

– phosphate

H231

– phosphite

C145

H230

Trimethylacetonitrile

C126

H212

H206


Index Terms

Links

Trimethylamine

C121

Trimethylborane

C147

2,2,4-Trimethylpentane

U405

Trimethylphenylammonium ion

H209

Trimethylphosphine

H229

– sulfide

H230

Trimethylsilane

H228

Trimethylsilyl compounds

40

Trimethylsilyloxyl compounds

41

H208

3-(Trimethylsilyl)-1-propanesulfonate

C159

H242

2,2,3,3-D4-3-(Trimethylsilyl)–propionate

C159

H242

Trimethylsulfonium iodide

C130

H216

Trimethylvinylsilane

C144

H228

1,3,5-Trioxane

C120

Triphenybismuth

C147

Triphenyl – phosphate

C146

– phosphite

C146

Triphenylamine

C123

Triphenylantimony

C147

Triphenylarsane

C147

Triphenylmethanol

H203

Triphenylphosphine

C146

– oxide

C146

Tripropylamine

C121

Tris(dimethylamino) phosphite

H230

Tris(dimethylamino) phosphine

C145

1,3,5-Trithiane

H215

Trithiocarbonates

C142

H227

I285

I302

M322

M332

Tropylium ion

I283

I284


Index Terms Tryptophan

Links C151

H235

Twistane

C94

Tyrosine

C150

H234

Ultramark

M374

M378

Unsaturated ketones

C135

Uracil

C154

H237

U404

Ureas

15

C143

H227

I301

12

14

C143

H227

I301

I302

U

I302 Urethanes – phenyl

43

Uridine

C154

UV/Vis spectroscopy

U385

V Valeraldehyde

C133

Valeric acid

C137

H221

δ-Valerolactam

C141

H225

δ-Valerolactone

C139

H223

Valeronitrile

C126

H212

Valine

C148

H233

– coupling

H166

H168

– glycols

M331

I276

Vicinal

Vinyl – acetate

H222

– alcohol

C118

– bromide

H200

– chloride

H199

– compounds

35

C83


Index Terms

Links

Vinyl (Cont.) – ethers

I249

I250

– fluoride

C112

H198

– formate

H221

– iodide

H201

– isocyanate

C127

– isocyanide

H213

Vinylphosphine

C145

H213

M334

I278

W Water

I312

Water-d2

M371

H242

X Xanthates

I284

Xanthone

H197

Xylene

U405

Xylose

H236

I285

Z Zwitterions Zinc compounds

I309 H183


1.1

Scope and Organization

1

1 Introduction

1.1 Scope and Organization The present data collection is intended to serve as an aid in the interpretation of molecular spectra for the elucidation and confirmation of the structure of organic compounds. It consists of reference data, spectra, and empirical correlations from 13C and l H nuclear magnetic resonance (NMR), infrared (IR), mass, and ultraviolet-visible (UV/vis) spectroscopy. It is to be viewed as a supplement to textbooks and specific reference works dealing with these spectroscopic techniques. The use of this book to interpret spectra only requires the knowledge of basic principles of the techniques, but its content is structured in a way that it will serve as a reference book also to specialists. Chapters 2 and 3 contain Summary Tables and Combined Tables of the most relevant spectral characteristics of structural elements. While Chapter 2 is organized according to the different spectroscopic techniques, Chapter 3 provides for each class of structural elements spectroscopic information obtained with various techniques. These two chapters should assist users that are less familiar with spectra interpretation to identify the classes of structural elements present in samples of their interest. The following four chapters cover data from 13C NMR, 'H NMR, IR, and mass spectroscopy, and are ordered exactly in the same manner by compound types. These cover the various skeletons (alkyl, alkenyl, alkynyl, alicyclic, aromatic, and heteroaromatic), the most important substituents (halogen, single-bonded oxygen, nitrogen, sulfur, and carbonyl), and some specific compound classes (miscellaneous compounds and natural products). Finally, a spectra collection of common solvents, auxiliary compounds (such as matrix materials and references) and commonly found impurities is provided for each method. Not only the strictly analogous order of the data but also the optical marks on the edge of the pages help fast cross-referencing between the various spectroscopic techniques. Although currently, UV/vis spectroscopy is only marginally relevant to structure elucidation, its importance might increase by the advent of high throughput analyses. Also, the reference data presented in Chapter 8 are useful in connection with optical sensors and the widely applied UV/vis detectors in chromatography and electrophoresis. Since a large part of the tabulated data either comes from our own measurements or is based on a large body of literature data, comprehensive references to published sources are generally not included. Whenever possible, the

2

1

Introduction

data refers to conventional modes and conditions of measurement. For example, unless the solvent is indicated, the NMR chemical shifts were determined usually with deuterochloroform or carbon tetrachloride as solvent. Likewise, the IR spectra were measured using solvents of low polarity, such as chloroform or carbon disulfide. Mass spectral data were recorded with electron impact ionization at 70 eV. While retaining the basic structure of the previous editions, numerous new entries have been added. Altogether, the amount of data has been more than doubled. The section on mass spectrometry (MS) is entirely new and contains a unique collection of fragmentation rules for the various compound classes. As a new feature, prototype IR spectra for each class of compounds schematically show the analytically relevant absorption bands. The Combination Tables of the earlier editions have been extended and arranged in two chapters, the first organized according to band positions and the second according to compound classes. The enclosed compact disc contains programs for estimating 13C and lH chemical shifts of organic compounds containing up to 15 non-hydrogen atoms. Both programs are available for Windows and Macintosh systems and require a Java environment for the graphical structure input. Technical details about the requirements and installation procedures are given in the corresponding ReadMe files. Extensive help files are available as part of the programs. In addition, the structure generator Assemble 2.0 (also limited to 15 non-hydrogen atoms) is available for Windows systems. Based on the molecular formula and available structural information, it is capable of generating all possible structural isomers. An extensive hypertext based tutorial describes its main features. It is especially recommended as a quality control tool to check if alternative solutions that also agree with the experimental data have gone unnoticed.

1.2

Abbreviations and Symbols

1.2 Abbreviations and Symbols al alk alken ar as ax comb d

aliphatic alkyl alkenyl aromatic asymmetric axial combination frequency doublet 6 IR: deformation vibration NMR: chemical shift DMSO dimethyl sulfoxide equatorial eq molar absorptivity E fragment Frag skeletal vibration Y geminal gem halogen hal in plane vibration iP coupling constant J molecular radical ion M+' mass to charge ratio m/Z fkquency V out of plane vibration OOP shoulder sh stretching vibration st symmetric SY TMS tetramethylsilane vicinal vic

3

2.1 General Tables

5

2 Summary Tables

2.1 General Tables 2.1. I

Calculation of the Number of Double Bond Equivalents from the Molecular Formula

General Equation:

2 + Z n i( v i - 2) double bond equivalents =

i

2

ni: number of atoms of element i in molecular formula vi: formal valence of element i

Short Cut:

For compounds containing only C, H, 0, N, S , and halogens, the following steps permit a quick and simple calculation of the number of double bond equivalents: 1. 0 and divalent S are deleted from the molecular formula 2 . Halogens are replaced by hydrogen 3. Trivalent N is replaced by CH 4. The resulting hydrocarbon, C,H,, is compared with the saturated hydrocarbon, CnHzn+2. Each double bond equivalent reduces the number of hydrogen atoms by 2: double bond equivalents =

2n+2-x 2

6

2 Summary Tables

2.1.2 Properties of Selected Nuclei

Isotope

1H 2H 3H 1OB 1lB

13c

I4N I5N 170

I9F 31P 33s 1 17sn

119sn 195Pt 199Hg 207Pb

Frequency Relative Relative Natural Spin abundane quantum [MHZ] at sensitivity sensitivity number, I 2.35 Tesla of nucleus at natural [%I abundance

99.985 0.015 0.000 19.58 80.42 1.108 99.635 0.365 0.037 100.000 100.000 0.76 7.61 8.58 33.8 16.84 22.6

112 1 112 3 312 112 1 112 512 112 112 312 112 112 112 112 112

100.0 15.4 106.7 10.7 32.1 25.1 7.3 10.1 13.6 94.1 40.5 7.6 35.6 37.3 21.5 17.8 20.9

Electric quadrupole moment [e x 10-24 cm21

1 1 9 . 6 ~ 1 0 - ~ 1 . 5 ~ 1 0 - ~2 . 8 ~ 1 0 - ~ 0 1.2 2 . 0 ~ 1 0 - ~3 . 9 ~ 1 0 - ~7 . 4 ~ 1 0 ' ~ 1 . 6 ~ 1 0 ' ~ 1.3~10-1 3 . 6 ~ 1 0 - ~ 1 . 6 ~ 1 0 - ~1 . 8 ~ 1 0 - ~ 1.0~10-3 1.0~10-3 1.9~10-2 1.0~10-3 3.8~10-6 2 . 9 ~ 1 0 - ~l . l ~ l O - -~2 . 6 ~ 1 0 ' ~ 8.3~10-1 8.3~10-1 6 . 6 ~ 1 0 - ~6 . 6 ~ 1 0 - ~ 2 . 3 ~ 1 0 - ~1 . 7 ~ 1 0 - -~6 . 4 ~ 1 0 - ~ 4 . 5 ~ 1 0 - ~3 . 4 ~ 1 0 - ~ 5.2x10-* 4 . 4 ~ 1 0 - ~ 9 . 9 ~ 1 0 - ~3 . 4 ~ 1 0 - ~ 5 . 7 ~ 1 0 - ~9 . 5 ~ 1 0 - ~ 9 . 2 ~ 1 0 - ~2 . l ~ l O - ~

2.2 13C NMR Spectroscopy

7

2.2 13C

NMR Spectroscopy

Summary of the Regions of Chemical Shifts, 6, for Carbon Atoms in Various Chemical Environments (6 in ppm relative to TMS. Carbon atoms are specified as follows: Q for CH3, T for CH2, D for CH, and S for C).

8

2 Summary Tables

2.2 13C NMR Spectroscopy

9

I3C Chemical Shifts for Carbonyl Groups ( 6 i n ppm relative to TMS) R -H -CH3 -CH2CH3 -CH(CH3)2 -C(CH3)3 -n-CgH17 -CH2Cl -CHC12 -CCl3 -cyclohexyl -CH=CH2 -CSH -phenyl

R -H -CH3 -CH2CH3 -CH(CH3 )2 -C(CH3)3 -n-CgH17 -CH2C1 -CHC12 -CCl3 -cyclohexyl -CH=CH2 -C

R- -C-ha1

Rearrangements

[M-20]+' rM-361"

HF elimination HC1 elimination

ha1 n+z*

I280 nm

For C-I; for C-Br and C-Cl in general only absorption tail, for C-F no absorption

(log E ~ 2 . 5 )

uv

56

3 Combination Tables

3.7 Oxygen Compounds 3.7.1 Alcohols and Phenols

Assignment ~ ~ C N Ma 1R c - O ~

Range 50-100 ppm

a1 C-(C-OH) 10-60 ppm a1 C-(C-C-OH) 10-60 ppm ar C-OH 135-155 ppm ar C-(C-OH) 100-130 ppm

l"MR

IR

alC-OH ar C-OH -CHz-OH -CH-OH ar CH-(C-OH)

0-H st

C-O(H) st

Ms

0.5-5 ppm 5-8 ppm 3 . 5 4 0 ppm 3.8-4.2 ppm 6.5-7.0 ppm

For C-aromatics, shift with respect to CH-(C-H): ortho -0.6 ppm, metu -0.1 ppm, pura = - O S ppm

3650-3200 cm-l Position and shape depend on degree of association; often different bands for Hbonded and free OH 1260-970 cm-I Strong

Molecular ion

Fragments

Comments Shift with respect to corresponding C-H: =+50 ppm Hardly any shift with respect to C-(C-CH3) Shift with respect to C-(C-C-CH3) -5 ppm Shift with respect to C-H =+25 ppm Shift with respect to C-(C-H): ortho -13 ppm, meta =+1 ppm, para -8 ppm Position and shape strongly depend on experimental conditions

Aliphatic: m/z 31, 45, 59,. [M- 18]+' w-331' [M-46]+' Aromatic: [ar-O]+' [M-281" (CO) [M-29]+ (CHO)

Aliphatic: weak, often missing for primary and highly branched alcohols; in this case, peaks at highest mass are often due to [M-l8]+'or [M-15]+ Aromatic: strong Primary: m/z 31 > m/z 45 = m/z 59 Secondary, tertiary: local maxima due to acleavage: R -R* + R-CH-OH R-CH=OH

+.

-

Generally accompanied by rearrangement peaks

3.7 Oxygen Compounds Assignment

Range

57

Comments Aliphatic: elimination of H20 from M+' and from products of a-cleavage; elimination of H 2 0 followed by alkene elimination Unsaturated: vinylcarbinols: spectra similar to those of ketones allyl alcohols: specific, aldehyde elimination:

Rearrangements

Aromatic: ortho effect with appropriate substituents:

-Y-Z: -CO-OR, -C-hal, -0-R, and similar

Aliphatic: no absorption above 200 nm Aromatic: in alkaline solution, shift to longer wavelength and intensity increase due to deprotonation

uv

3.7.2 Ethers Assignment a1 C-0 a1 C-(C-0) a1 C-(C-C-O)

o-c-0

(C)=C-o C=(C-o) ar c-0 ar c-(c-0)

Range 50-100 ppm 10-60 ppm 10-60 ppm 85-1 10 ppm 115-165 ppm 70-120 ppm 135-155 ppm 100-130 ppm

Comments 1 3 c NMR Oxiranes: outside the normal range Hardly any shift with respect to C-(C-CH3) Shift with respect to C-(C-C-CH,) -5 ppm Shift with respect to (C)=C-C =+15 ppm Shift with respect to C=(C-C) -30 ppm Shift with respect to C-H =+25 ppm Shift with respect to C-(C-H): ortho -15 ppm, meta =+1 ppm, para = -8 ppm

58


Assignment ~"MR~ ~ 3 - 0 CH2-0 0-CH2-0 CH-0 CH-03 H-C(O)=C H-C(=C-O) ar CH4C-O)

IR

H-C(-0) st

Range 3.3-4.0 ppm 3.4-4.2 ppm 4.5-6.0 ppm 3.5-4.3 ppm 4 - 6 ppm 5.7-7.5 ppm 3.5-5.0 ppm 6.6-7.6 ppm

2880-2815 cm-l

H-CH(-O):! st 2880-2750 cm-l C-O-C st as 1310-1000 cm-l

lcls

Shift with respect to H-C(H)=C =+1.2 ppm Shift with respect to H-C(=C-H) -1 ppm

For CH3-O and CH2-O; similar range for amines Two bands Strong, sometimes two bands Aliphatic: weak, tendency to protonate Aromatic: strong

Molecular ion Fragments

Comments Singlet

Aliphatic:

m/z 31, 45, 59, ...

[M- 18]+' [M-33]+ [M-46]+'

Base peak of aliphatic ethers, generally due to fragmentation of the bond next to the ether bond:

+.

Ri-C-O-R2]

-R1'

+

C=O-R2

or due to heterolytic cleavage of the C-0 bond, especially for polyethers:

Aryl alkyl ethers: preferential loss of the alkyl chain Diary1 ethers: preferential loss of CO (28) from M+' and/or [M-H]+ as well as: ar 1- D G r 2

Rearrangements

Aliphatic: elimination of alcohol Aromatic ethyl and higher alkyl ethers: alkene elimination to the phenol:

Y

W

1+*

Aliphatic: no absorption above 200 nm Aromatic: shift to higher wavelength and more intense due to the ether group

1+*

3.8 Nitrogen Compounds

59

3.0 Nitrogen Compounds 3.8.1 Amines Assignment a1 C-N a1 C-(C-N) a1 C-(C-C-N) (C)=C-N C=(C-N) ar C-N ar C-(C-N)

Range 25-80 ppm 10-60 ppm 10-60 ppm 120-170 ppm 75-125 ppm 130-150 ppm 100-130 ppm

Comments Shift with respect to C-H = +20 to +30 ppm 13C N M R Shift with respect to C-(C-C) =+2 ppm Shift with respect to C-(C-C-C) =-2 ppm Shift with respect to (C)=C-C =+20 ppm Shift with respect to C=(C-C) -25 ppm Shift with respect to C-H =+20 ppm Shift with respect to C-(C-H): ortho -15 ppm, meta =+1 ppm, para =-10 ppm

a1 C-NH ar C-NH a1 or ar N+H CH3-N CH2-N CH-N CH-N+ ar CH-(C-N)

0.5-4.0 ppm 2.5-5.0 ppm 6.0-9.0 ppm 2.3-3.1 ppm 2.5-3.5 ppm 3.0-3.7 ppm 3 . 2 4 . 0 ppm 6.0-7.5 ppm

1H N M R

ar CH-(C-N+)

7.5-8.0 ppm

N-H st

3500-3200 cm-l

N+-H st

3000-2000 cm-l

N-H 6 N+-H 6 H-C(-N) st

1650-1550 cm-l 1600-1460 cm-l 2850-2750 cm-l

Often broad Singlet

For C-aromatics, shift with respect to CH-(C-H): ortho -0.8 ppm, meta -0.2 ppm, para -0.7 ppm For C-aromatics, shift with respect to CH-(C-H): ortho =+0.7 ppm meta =+0.4 ppm, para =+0.3 ppm Position depends on extent of association, often different bands for H-bonded and free NH; always at least two bands for NH2 Broad, similar to COOH band but more structured Weak or absent Often weak For CH3(-N) and CH2(-N); similar range for ethers

IR

60

Ms


Assignment Molecular ion

Fragments

Range

Comments Odd mass number for odd number of nitrogens Aliphatic: weak, tendency to protonate Aromatic: strong, no tendency to protonate [M+H]+ is often important Aliphatic: Base peak of aliphatic amines generally due to dZ 30, 44, 58,... fragmentation of the bond next to the amine bond:

Elimination of alkenes following amine cleavage:

Rearrangements

Aliphatic: no absorption maximum above 200 nm Aromatic: in acidic solution, shift to lower wavelength and decrease in intensity

W

3.8.2 Nitro Compounds Assignment Range 13CNMR alC-N02 55-1 10 ppm a1 C-(c-N02) 10-50 ppm a1 c-(ccN02) 10-60 ppm ar C-NO2 130-150 ppm ar C-(C-N02) 120-140 ppm

lH N M R

IR

a1 CH-NO2 ar CH-(C-NOz)

NO2 st as NO2 st sy

4.2-4.6 ppm 7.5-8.5 ppm

1660-1490 cm-l 1390-1260 cm-l

Comments Shift with respect to C-H =+50 ppm Shift with respect to C-(C-C) -6 ppm Shift with respect to C-(C-C-C) -2 ppm Shift with respect to C-H =+20 ppm Shift with respect to C-(C-H): ortho =-5 ppm, meta -+1 ppm, para =+6 ppm

For C-aromatics, shift with respect to CH-(C-H): ortho =+1.O ppm, meta =+0.3ppm, para =+0.4 ppm Strong to very strong Strong to very strong


Assignment Molecular ion

Range

Fragments

[M-16]+', [M-46]+ m/z 30, [M-17]+, [M-30]+, [M-471"

Rearrangements

61

Comments Odd mass number for odd number of nitrogens Aliphatic: weak or absent Aromatic: strong

=275 nm (log E 3)

f.

Saturated aldehydes a$-Unsaturated aldehydes Aromatic aldehydes

f. W

64


3.1 0.2

Ketones Assignment

Range '3cNMR c=o 195-220 ppm a1 C-(C=O) 25-70 ppm al C-(C-C=O) 5-50 ppm (C)=C-(C=O) 105-160 ppm C=(C-C=O) 105-160 ppm ar C-(C=O) 120-150 ppm

Comments

lH NMR

CH-CO-al2.0-2.6 ppm CH-CO-ar 2.5-3.6 ppm

al CH-(C=O)

2.0-3.6 ppm

CH=CH-(C=O) 5.5-7.0 ppm ar CH-(C-C=O) 7.2-8.0 ppm

IR

c=ost

MS

Molecular ion

1775-1650 cm-l

For C-aromatics, shift with respect to CH-(C-H): ortho =+0.6 ppm, meta =+O. 1 ppm, para =+0.2 ppm Aliphatic: ~ 1 7 1 cm-l 5 Cyclic: ring size 26: ~ 1 7 1 cm-l 5 ring size 3)

Aliphatic esters a$-Unsaturated esters Aromatic esters

Ms

68


3.1 0.5 Carboxylic Amides and Lactams

Assignment

Range 165- 180 ppm l3CNMR CONR2 a1 C-(CONR2) 20-70 PPm a1 C-(C=( 121.3

\=( 125.1 117.6 c1 63.7

40.7

88.9

CC13 CH2C1’fE7.

cHc12YE.4

0

FL59.8 25.4

126.6

128.5

135.5

__

124.3 n : ! 8 128.4 130.3

148.4

N

129.7 138.7

122.3 m 149.5

149.8

OH

y167.0 0

0

0;;:;

7

CCly-CC13

96.2

117.2

2

105.3

YcE 1 1

a-cl

c1

34.6

27.3

C

.

N

t

5

cl

151.6

4.7 Halogen Compounds

115

4.7.3 Bromo Compounds 13C Chemical Shifts of Bromo Compounds ( 6 in ppm relative to TMS)

9.6

21.4

12.1

-28.7

CH3Br

CH2Br2

CHBr3

CBr4 36.4

19.4

\Br 13.0

27.6

X Br.

1

Br-Br

53.4

CBr3--CBI~

31Y5 F r

Br

127.2

114.7

=( 97.0

Br.

Br

109.4

w

116.4

Br

Hal 25.9

"50.

112.4

B~

1

Br

122.4

+Br

E

49.4

32.4

31.8

Y

35.6

"k"g;.7 Br Br

31.3

0

0

128.7 138.5

Br

122.6 m 8 3 . 150.3

N

t

Br

142.3

4 13C NMR

116

4.7.4 lodo Compounds I3C Chemical Shifts of Zodo Compounds ( 6 in ppm relative to TMS)

-24.0 CH3I 20.6 -1 -1.6 3.O

&J

d31.2 40.1 28.3

-292.5 CI4 40.4

31.2

27.0 -1

I

I

130.1

25.4

127.4

I

144.8

Xi.0

y i . 9

15.3 9.1 130.3 -1 85.2

I1-

I. mi

-139.9 CHI3

-54.0 (33212

I

79.4

u 96.5

11-

@j mO .: 127.6

-

126*o0 / 6 5 . 2 150.1 N ‘ 156.9

137.6

122.9 150.8

N

t

118.2

4.7.5 References [l] G.R. Somayajulu, J.R. Kennedy, T.M. Vickrey, B.J. Zwolinski, Carbon-13 chemical shifts for 70 halomethanes, J. Magn. Reson. 1979,33, 559. [2] A. Furst, W. Robien, E. Pretsch, A comprehensive parameter set for the prediction of the 13C NMR chemical shifts of spjl-hybridized carbon atoms in organic compounds, Anal. Chim. Acta 1990,233, 213. [3] D.W. Ovenall, J.J. Chang, Carbon-13 NMR of fluorinated compounds using wide-band fluorine decoupling, J. Magn. Reson. 1977,25, 361.

4.8 Alcohols, Ethers, and Related Compounds

117

4.8 Alcohols, Ethers, and Related Compounds 4.8.1 Alcohols

13C Chemical Shifts of Aliphatic Alcohols ( 6 in ppm relative to TMS) 50.2 CH30H

18.2 \/OH 57.8

15.2 36.0 -OH 20.3 62.9

31.2

14.2 31.9 32.9 O H 23.0 25.8 62.1

25.9 /\/OH 10.3 64.2

YE

25.3

23.8 33.6 O -H 15.3 29.4 63.2

26.2 73.3 14.3 39.4 30.5 10.1 19.2 OH 72.2

7

1 4 s 6 7 . 2 23.2 39.2 23.5

13C Chemical Shifts of Aliphatic Glycols and Polyols (6 in ppm relative to TMS) HOWOH 63.4

HO\/\/OH 36.4

68.2

60.2

...........

7

2b OH . 7

18.7 ‘, 23.0 a

H

‘3

0

in CDCl,,

76.1

x

~

67.7 ’, 71.6 in D,O

72.9

HO 73.7

48.3 64*3 74.3

74.5

66.0 H O Y d ! ? H 91.2 OH

H Y % . 3 OH

~

~

4 13C NMR

118

13C Chemical Shifts of Alcohols ( 6 in p p m relative to TMS)

125.1

99.1

CF3-0H 61.4 '[Jlc~ 278 HZ *1J1,, 35 Hz

CC13-0H 75.9

OH

63.4 _TOH 114.9 137.5

8ti.8

73.8 83.0

OH

QH

121.1

108.5

50.0

25.1

26.3

13C Chemical Shifts of Enols ( 6 in ppm relative to TMS)

-pH 88.0

1 9 0 . a 9 0 . 5

149.0 22.5

0

32.8

1

46.2 103.3

99.0 22.5 31.0

A :::;

28.3 46.2

UFa6

0

57.3

J&Ol.l 56.6

28.5


119

4.8.2 Ethers 13C Chemical Shifts of Ethers ( 6 i n p p m relative to TMS)

60.9 \

57.6 67.7

59.1

74.5 10.5

54.9 k . 6

/

0

\0-

\0-

14.7

23.2

59.1 73.4 20.5

\

27.0

49 Jtrans

b 7'01 a 0.92

0

At-lOO'C: Ha, 1.1

In derivatives: 3Jab 1.5 to 2.0 3Jbc 0.5 to 1.5

io

ed0~5*66 2Jgem,a -12.8 b 2.27 3Jab,cis 9-3 a 3Jab,trans 5*7 1.79 2Jgem,., -16.1 3Jbc 2.3

a 6-53 b 6.22

3Jab 5.1 5Jac 0.5 5Jad 1.4 5.85 4Jae 1'3 3Jaf 2.0

01.94

In derivatives: 2Jgem -10 to -17 3J,is 4 to 12 3Jp,, 2 to 10 4Jcis =O 4Jpans -1

.44 In derivatives:

In derivatives:

lS1 2Jgem -8 to -18 3Jcis 5 to 10 3Jtrans 5 to 10

c

*

4Jbd 5Jbe,cis -2'3 2*1 5Jbe,trans 3*0 5.8 3Jcd

4Jbc -0.2 4Jbd -0.4 4Jbe 2.0 2Jcd O''

2Jgem -11 to -14 3J,x,ax 8 to 13 3 Jeqm 2 to 6 3~e9,eq 2 to 5 Generally: Jeq,ax Jeq,eq + 1

b 5.95

,13.7 1.o -0.3 1.8 4.6 2.8

a 2.57

3Jab

1.3

edoc;;3i8 a

2.80

4Jbd 1.1 5Jbe 2.0 3Jcd 1.9

5.59 3Jab =lo 1.96 3Jbc d

1.65

1.5

5.4 Alicyclics b 5.71

0 C

177 3Jab=10

2.11 3Jbc 3*7

d 2.62

e

2.49

6 6 . 5 0 3Jab 11.2 5J,g -0.6 c 6.09 4Jac o.8 3Jde 0 3Jbc 5.5 4Jdf f e d 5.26 3Jcd 8.9 5Jdg 0 2.22 5Jcf 0 2Jgem,e -13.0

a

b5.56 3Jab=10 C 2.1 1 3Jbc 5.3

0

0.5

1.47 f

e 2.14

1.44

4J1,4 1.2 4J1,5n -0.3 4 J i , 5 ~ 0.2 3 ~ 1 , 6 n 0.1 3 ~ 1 , 6 x 4.7 J I ,7a 1*2 3J1,7s 1.6 2J3n,3x -17.6 3J3n,4 0 4J3n,7a 4.2 ~ 3 n , 7 a 4.2 3J3x,4 4.8 4J3x,5x 2.3 3 ~ 4 , 5 n 0.1 3J4,5x 4.3

-0.5 4J4,6x 0.7 3 ~ 4 , 7 a 2.1 3J4,7s 1.6 2J5n,5x -12.8

4J4,6n

3J5n,6n 9*1 3J5n,6x 4.7 ~5 n ,7a -0.1 ~5 n ,7 s 2.1 3J5x,6n 4.6 3J5x,6x 12e1 2J6n,6x -12.3 J6n,7 a 4J6n,7s 2.3 2J7a,7s -10.2

5 'H NMR

178

In condensed alicyclics, couplings over four or more bonds are often observed. Such long-range couplings are particularly large if the arrangement of the bonds between the two protons is w-shaped: 4Jac = 7 =0 4 J a ~4Jbd ,

H H CH3 signal broadened due to longrange coupling

HC

0

H Chemical Shifts and Coupling Constants of Monosubstituted Cyclopropanes (6 in ppm relative to TMS, J in Hz)

Substituent X -H C -CH=CH2 -phenyl H -F a -C1 1 -Br -1 0 -OH N -NH2 -CN 0 -CO-cyclopropyl 11 -COOH C -COOCH3 / \-COF -coc1 -Li -B(cyclopropyl)2 -Hg-cyclopropyl

Ha

0.20 2.36 1.71 4.32 2.55 2.83 2.31 3.35 2.23 1.36 1.70 1.59 1.95 1.66 2.11 -2.53 -0.25 0.00

Hb,d 0.20 0.64 2.65 0.69 0.87 0.96 1.04 0.59 0.32 0.94 0.56 0.91 0.81 1.20 1.18 0.43 0.66 0.75

H ~ , e 3Jab 3Jac 2Jbc 0.20 9.0 5.6 -4.3 0.34 8.2 4.9 -4.5 2.83 9.5 6.3 -4.5 0.27 5.9 2.4 -6.7 0.74 7.0 3.6 -6.0 0.81 7.1 3.8 -6.1 0.76 7.5 4.4 -5.9 0.34 6.2 2.9 -5.4 0.20 6.6 3.6 -4.3 0.93 8.4 5.1 -4.7 1.02 7.9 4.6 -3.5 1.05 8.0 4.6 -4.0 0.85 8.0 4.6 -3.4 1.11 8.0 4.6 -4.5 1.28 7.9 4.4 -4.5 -0.12 10.3 9.1 -1.6 0.61 8.9 5.8 -3.3 0.47 9.6 6.9 -3.7

3Jbd

9.0 9.3 9.5 10.8 10.3 10.2 9.9 10.3 9.7 9.2 9.1 9.3 8.8 10.1 9.2 7.7 8.2 8.5

3Jbe 5.6 6.2 5.2 7.7 7.1 7.0 6.6 6.8 6.2 7.1 7.0 7.1 6.9 7.5 7.6 3.2 5.9 4.8

3Jce 9.0 9.0 8.9 12.0 10.6 10.5 10.0 10.9 9.9 9.5 9.5 9.7 9.6 9.3 10.0 6.5 8.4 7.9

5.4 Alicyclics

179

H Chemical Shifts of Axially and Equatorially Monosubstituted Cyclohexanes (6 in p p m relative to TMS)

Substituent R

-D C -CHq -pheiyl H a -Br 1 -I 0 -OH -0COCH3 N -NH2 -NHCH3 -NO2 S -SH

2e

3a

3e

la

2a

1.12 1.27 2.47 3.63 3.81 3.98 3.38 4.46 2.52 2.08 4.23 2.57

1.12 1.60 1.12 1.60 0.81 1.57 1.15 1.60

1.09 1.78 1.19 1.61

2.2 0.7

1.9 1.3

le

2a

2e

3a

3e

1.60 1.93 2.98 4.34 4.62 4.72 3.89 4.98 3.15 2.70 4.43 3.43

1.12 1.60 1.12 1.60 1.37 1.40 1.39 1.34 1.7 1.35 1.58 1.58 1.33 1.47 2.3 1.6 2.6 1.5 1.9

0

180

5 'H NMR

5.5 Aromatic Hydrocarbons IH Chemical Shifts and Coupling Constants of Aromatic Hydrocarbons ( 6 in ppm relative to TMS, J in Hz) In derivatives: 0 7 . 2 6 3~0d0 6.5-8.5 4J,eta 1.O-3.0 5Jpara 0.0-1 .O

7.67 g~ f \

e

7.98

e 8.40

d

d

In derivatives: 3Jab 8-9 5Jae ~ 0 . 9 87.32 4Jac 6Jaf =-Oal 5Jad 5Jag =0.2 35bc 5-7 4Jah=-0.5 7Jbf ~ 0 . 3 6Jbg ~ 0 . 1

In derivatives: 7.44 3Jab 8*5-9*5

;

4Jac 0.8-1.5 5Jad 0.6-0.9 5Ja, 10.8 3Jbc 6.5-8.0 4Jde 10.4

b7.61

3Jab

8.4

f

In derivatives: 3Jef 4

In routine spectra, the small long-range couplings between aromatic protons and aliphatic substituents are not resolved. Nevertheless, they are diagnostically highly relevant because the line broadenings caused by them are easily detected (if there is a reference line in the spectrum, e.g. from another methyl group, or in an AA'XX' spin system of the aromatic protons). As a confirmation, a decoupling experiment may be useful (line sharpening on weak irradiation of the frequency of the coupling partner) or a COSY experiment is recommended.

5.5 Aromatics

181

CH3 ,CH31.25

FH31.32 CH3-C-

CH3

6

7.28 7.18

7.08

7.09

7.05

& 6*99a 7.08

c 3.33

2.91

2.04

\

3Jab 5.8

7.01 2.85

b 6.50 4Jac 'Jad 0.7 2.0 6

.

9

3

a 1.60

\

8

6*82

3Jbc 2.0

3.91 7.31 7.38 \

7.19

3.87 \ 7.55 7.28 A

7.75 2 -\7.29 7.22 3

- a 7.15 ad

d 7.46

d 7.79

4Jbd 0.6 3Jcd

182

5

'H NMR

Effect of Substituents on H Chemical Shifts of Monosubstituted Benzenes (in ppm relative to TMS)

Substituent X -H C -CH3 -CH2CH3 -CH(CH3)2 -C(CH3)3 -CF3 -CC13 -CH20H -CH=CH2 -CH=CH-phenyl (trans) -CZCH -C eC-phenyl -phenyl -2-pyridyl -

H -r

a -C1

I -Br -I 0 -OH -OCH3 -OCH2CH=CH2 -0-phenyl -0COCH3 -0CO-phenyl -0SO2CH3 N -NH2 -NHCH3 -N(CH3)2 -N+(CH3)31-NHCOCH3 -NHNH2 -N=N-phenyl -NO -NO2 -CN -NCS

z2

z3

z4

0.00 -0.20 -0.14 -0.13 0.03 0.19 0.55 -0.07 0.04 0.16 0.16 0.20 0.22 0.73 -0.29 0.01 0.17 0.38 -0.53 -0.49 -0.45 -0.34 -0.19 -0.1 1 -0.05 -0.80 -0.83 -0.67 0.72 0.38 -0.60 0.67 0.55 0.93 0.25 -0.11

0.00 -0.12 -0.05 -0.08 -0.08 -0.07 -0.07 -0.07 -0.05 0.00 -0.03 -0.04 0.06 0.09 -0.02 -0.06 -0.11 -0.23 -0.17 -0.11 -0.13 -0.04 -0.03 0.07 0.07 -0.25 -0.22 -0.18 0.40 -0.02 -0.08 0.20 0.29 0.26 0.18 0.04

0.00 -0.21 -0.18 -0.18 -0.20 0.00 -0.09 -0.07 -0.12 -0.15 -0.02 -0.07 -0.04 0.02 -0.23 -0.12 -0.06 -0.01 -0.44 -0.44 -0.43 -0.28 -0.19 -0.10 -0.01 -0.64 -0.68 -0.66 0.34 -0.26 -0.55 0.20 0.35 0.39 0.30 -0.02

5.5 Aromatics

Substituent X S -SH -SCH3 -,%phenyl -S-S-phenyl -SOzCH3 -S020CH3 -s02c1 -S02NH2 0 -CHO 11 -COCH3 C -COCH2CH3 / \ -CO-phenyl -CO-(2-~yridyl) -COOH -COOCH(CH3)2 -COO-phenyl -CONH2 -COF -coc1 -COBr -CH=N-phenyl -Li -MgBr -Mg-phenyl -Si(CH& -Si( phenyl)&l -Sic13 P -Pb(phenyl)2Cl -P(PhenY 112 -PO(OCH3)2 -Zn-phenyl . -Hg-phenyl

z2 -0.08 -0.08 -0.06 0.24 0.68 0.68 0.68 0.59 0.61 0.60 0.63 0.44 0.86 0.87 0.73 0.88 0.69 0.71 0.81 0.77 0.64 0.77 0.40 -0.49 0.19 0.32 0.52 0.68 -0.02 0.46 -0.36 0.00

z3

-0.16 -0.10 -0.20 0.02 0.35 0.34 0.23 0.32 0.25 0.11 0.08 0.10 0.1 1 0.21 0.1 1 0.15 0.18 0.21 0.21 0.21 0.24 0.26 -0.19 0.18 0.00 0.07 =0.2 0.28 -0.33 0.14 0.02 0.00

z4 -0.22 -0.24 -0.26 -0.06 0.39 0.36 0.34 0.32 0.35 0.19 0.18 0.19 0.20 0.34 0.20 0.25

0.25 0.38 0.37 0.38 0.24 -0.29 -0.26 0.25 0.00 0.12 =0.2 0.11 -0.33 0.22 0.05 -0.20

183

184

5

'H NMR

Effect of Substituents in Position 1 on the IH Chemical Shifts of Monosubstituted Naphthalenes (in ppm relative to TMS)

0

Substituent X C -CHq -CH;CH3 -CH2CtCH -CH$1 -CF3 -

H -r a -C1 1 -Br

-I 0 -OH -OCH3 -0C0CH3 N -NH2 -N(CH3)2 -NHCOCH3 -NO2 -NCO -CN 0 -CHO 11 -COCH3 C -COOH / \ -COOCHq-

-coc1

*

H-2 -0.22 0.01 0.25 0.13 0.67 -0.22 0.17 0.38 0.10 -0.68 -0.68 -0.15 -0.77 -0.30 0.40 0.80 -0.29 0.48 0.44 0.38 1.11 0.80 1.17

Assignment uncertain

H-3 -0.13 0.08 -0.07 0.01 0.15 0.01 -0.04 -0.09 -0.48 -0.15 -0.09 0.11 -0.17 0.03 0.17 0.14 -0.15 0.12 0.10 -0.07 0.23 0.05 0.17

H-4 -0.16 0.03 -0.06 0.09 0.18 -0.11 -0.02 0.03 0.18 -0.36 -0.38 -0.10 -0.51 -0.19 0.05 0.19 -0.19 0.30 0.21 0.10 0.42 0.22 0.37

H-5 -0.03 0.17 0.00 0.13 0.23 0.13 0.07 0.05 -0.20 0.01 -0.01 0.03 -0.06 0.11 0.26 0.33 -0.03 0.16 0.06 0.01 0.24 0.08 0.17

H-6 -0.03 0.14 0.03 0.14 0.23 0.15" 0.11 0.11 -0.07 0.03 0.04 -0.07 -0.02 0.13 0.20 0.21 0.05 0.22 0.14 0.04 0.25 0.10 0.21

H-7 H-8 -0.01 0.10 0.17 0.38 0.13 0.69 0.20 0.42 0.29 0.52 0.17* 0.42 0.16 0.54 0.19 0.51 -0.02 0.27 0.06 0.41 0.03 0.50 0.07 0.16 -0.01 -0.01 0.10 0.55 0.24 0.44 0.32 0.72 0.03 0.24 0.29 0.51 0.23 1.52 0.13 1.08 0.34 1.43 0.20 1.30 0.30 1.04

5.5 Aromatics

185

Effect of Substituents in Position 2 on the lH Chemical Shifts of Monosubstituted Naphthalenes (in ppm relative to TMS)

Substituent X C -CH3 -CH2CH3 -CH(CH3)2 -CH=CH2 -CF3

-c1

-Br 0 -OH -OCH3 -0COCH3 N -NH2 -N(CH3)2 -NHCOCH3 -NO2 -CN 0 -CHO 11 -COCH3 C -COOH /\-COOCH3

-coc1

H-1 -0.21 -0.05 -0.07 0.06 0.45 0.13 0.23 -0.69 -0.70 -0.19 -0.88 -0.90 0.50 0.98 0.51 0.62 0.76 1.00 0.83 1.02

H-3 -0.14 0.02 0.01 0.30 0.30 0.08 0.14 -0.35 -0.28 -0.14 -0.56 -0.33 0.14 0.82 0.25 0.61 0.69 0.73 0.66 0.74

H-4 -0.06 0.09 0.05 0.11 0.23 0.07 -0.09 -0.05 -0.07 0.01 -0.16 -0.13 0.07 0.18 0.20 0.23 0.19 0.37 0.09 0.39

H-5 0.01 0.12 0.07 0.11 0.12 -0.08 -0.04 -0.03 0.06 -0.12 -0.12 0.06 0.18 0.19 0.21 0.17 0.36 0.09 0.49

H-6 -0.04 0.08 0.04 0.10 0.25 0.13 0.05 -0.11 -0.11 -0.04 -0.23 -0.23 0.07 0.28 0.31 0.30 0.25 0.36 0.15 0.32

H-7 -0.01 0.12 0.06 0.12 0.22 0.15 0.07 -0.02 0.00 0.11 -0.09 -0.08 0.10 0.24 0.26 0.24 0.21 0.32 0.11 0.37

H-8 -0.03 0.10 0.07 0.11

0.05 0.01 -0.14 -0.07 0.08 -0.23 -0.16 0.08 0.26 0.19 0.29 0.26 0.48 0.17 0.37

5 ’H NMR

186

5.6

Heteroaromatic Compounds 5.6.1

Non-Condensed Heteroaromatic Rings ‘ H Chemical Shifts and Coupling Constants of Non-Condensed Heteroaromatic Compounds ( 6 in ppm relative to TMS, IJI in H z )

4Jb, 2.3 b7.09 3Jab 0.8 b7.13 3Jab 1-2 a 7.70 4Jac c n a 7.69 4Jac O S c a7.13 4Jac 1-2 4Jbc 0.0 7.70 N 3Jbc Se 4Jad 2.5 7.95 0 3Jbc 3.6 Hd 13.4 (J values in derivatives) b 7.12 3Jab 5.4

‘0

d

0

l a 1

;gba ‘qb

8.15

3Jab 1.7 7.55 6.25 3Jab 2.1 4Jac 0.3 4Jac 0.0 4Jbc 1.8 y N a7.55 3Jbc 2.1 0 8.39 H d 13.7 (in CS,)

8.56 19b7.26 S

6.28

3 :abJacc0.4 4.7

a8.72 3Jbc 1.7

H 12

N-N

c(

8.27 N H 13.5 -12 (in H2S04)

5.6

In DMSO:

7.64 b 7.25

(in CDCl3)

7.32

a 8.59 7*38 7'75

3Jab 6.5

C

d e

b 7.40 4JaC 5Jad 0.6 'a 8 * l 9 4Jae 1.9 3Jbc 7.7 f 4Jbd 2.1 0

In denvatives: 3Jab 6.0 4-6 4Jac 1.9 0-2.5 5Jad 0.9 0-2.5 4Jae 0.4 0-0.6 3J13c7.6 7-9 4Jbd 1.6 0.5-2

'9 N,

/

Heteroaromatics

187

'6 9.04

3Jab 6.0 b8.50 4JaC 1'6 5Jad 0.8 e a9.23 45 ae 1.0 N 3Jbc 7.9 H 4Jbd 1.4 (in CD3CN)

7.22 1.o

b7'55 a9.24

0

5 'H NMR

188

Effect of Substituents on the IH Chemical Shifts substituted Furans (in ppm relative to TMS)

of Mono-

6H-2 = 7.38 + zi,2 6H-3 = 6.30 + zi,3 6H-4 = 6.30 + zi,4 ~ H - S= 7.38 + Zi,5

Substituent

in position 2 or 5 : '23 z54

-H

'25 z52

'32 z45

'34 z43

z35 z42

0.00

0.00

0.00

0.00

-0.42 -CH20H -0.11 -CH2NH2 -0.24 -CH=CHCHO 0.70 -Br -0.02 0.12 0&H3 -1.34 N -NO2 1.21 -CN 0.85 S -SCH3 -0.12 -SCN 0.40 0 -CHO 0.93 II -COCH3 0.81 C -COCF3 1.34 / \ -COOH 0.94 -COOCH3 0.85 -coc1 1.20

-0.12

-0.17 -0.08 -0.10 0.42 -0.01 -0.01 -0.68

-0.27

0.00 -0.17

0.00 -0.15

-0.13 -0.46

0.04 -0.28

-0.22 -0.37

0.45 -0.18 0.19 0.48 0.46

0.22 -0.05 0.19 0.37 0.36

-0.02 -0.15 0.03 -0.07 -0.12

0.89 0.45

0.54 0.33

0.36 -0.14

C -CH3

0

'24 z53

in position 3 or 4:

-0.05 -0.06 0.35 0.03 -0.13 -0.23 0.55

0.51

0.32 -0.06 0.06 0.31 0.23

0.28 -0.09 0.10 0.34 0.19 0.64 0.41 0.25 0.48

0.50 0.33 0.22 0.39

5.6

Heteroaromatics

Effect of Substituents on the I H Chemical substituted Pyrroles (in ppm relative to TMS)

Substituent in position 1 -H -CH3 -CH2CH3 -CHz-phenyl -phenyl -COCH3 -CO-phenyl

Substituent

C N

S 0

11

C

'15

z13 z14

0.00 -0.25 -0.16 -0.12 0.33 0.56 0.57

0.00 -0.13 -0.12 -0.04 0.14 0.12 0.18

in position 2 or 5: z23 254

-H -CH3 -NO2 -CN -SCH3 -SCN -CHO -COCH3 -COOCHq

212

0.00 -0.33 1.06 0.83 0.18 0.48 0.93 0.78 0.79

z24

253 0.00 -0.16 0.24 0.23 0.05 0.10 0.27 0.10 0.13

Shifts

189

of Mono-

in position 3 or 4: z25 z5 2

z32 z45

z34 z43

z35

0.00 -0.26 0.43 0.5 1 0.10 0.28 0.61 0.44 0.29

0.00 -0.34 1.04

0.00 -0.20 0.70

0.00 -0.20 0.13

0.79 0.90

0.63 0.73

0.15 0.16

z42

5

190

'H NMR

Effect of Substituents on the I H Chemical Shifts substituted Thiophenes (in p p m relative to TMS)

4032

5

Substituent

-H

C -CH3 -C%CH

H -c1 a -Br

N -NH2 -NO2 -CN S -SH -SCH3 -S02CH3

-soy21 -SCN

0 -CHO

11

-COCH3

C -COOH / \ -COOCH3

-coc1

S

Mono-

5H-2 = 7.20 + zi,2 6 ~ -= 3 6.96 + Zi,3 6 ~ -= 4 6.96 + Zi,4 6 ~ =~7.20 5 + Zi,5

in position 2 or 5:

in position 3 or 4:

z23 z54

z24 z53

z25 z52

0.00 -0.36 0.15 -0.25 -0.05 0.13 -0.72 -0.94 -0.95 0.82 0.47 0.00 -0.03 1.03 0.73 0.30 0.65 0.57 0.80 0.70 0.88

0.00 -0.24 -0.16 -0.22 -0.27 -0.33 0.59 -0.43 -0.45 -0.03 0.00 -0.20 -0.18 0.20 0.06 -0.05 0.10 0.00 0.08 -0.05 0.06

0.00 -0.29 -0.12 -0.22 -0.11 0.01 -3.10 -0.82 -0.85 0.30 0.28 -0.07 -0.05 0.79 0.45 0.28 0.45 0.28 0.40 0.20 0.44

* Present in the keto form

of

z45

z34 z43

z35 z42

0.00 -0.45

0.00 -0.22

0.00 -0.14

-0.22 -0.12 0.06

-0.11 -0.08 0.00

-0.03 -0.10 -0.19

-1.10 -1.25 0.95 0.63 -0.22 -0.33 0.96

-0.38 -0.53 0.60 0.20 -0.20 -0.10 0.48

-0.20 -0.25 0.03 0.15 -0.10 -0.03 0.46

0.25 0.79 0.68 0.99 0.78 1.05

0.05 0.45 0.47 0.48 0.47 0.50

0.05 0.03 -0.02 0.24 -0.05 0.03

z32

5.6

Heteroaromatics

Effect of Substituents on the I H Chemical Shifts of substituted Pyridines (in p p m relative to TMS; solvent: DMSO) 6H-2 = 8.59 + zi,2 6H-3 = 7.38 + zi,3

4

6H-6 = 8.59 + zi,6 Substituent in position 2 or 6 -H C -CH3 -CH2CH3 -CHz-phenyl -CH20H -CH2NH2 -CH2S-n-C3H7 -CH2S02-phenyl -CH=CH2 -phenyl -2-pyridyl .. H SF a -C1 1 -Br 0 -OH -0-n-CqHg N -NH2 -NHCOCH3 -NHCOOCH2CH3 -"NO2 -NO2 -CN S -SCH3 0 -CHO 11 -COCH3 C -CO-phenyl / \ -COOH -COO-n-CqHg -CONH2 -CSNH2 -CH=NOH

z23 z65 0.00 -0.11 -0.09 0.12 0.37 0.20 0.04 4 0.1 1 0.16 1.12 -0.10 0.32 0.41 -0.7 -0.53 -0.68 0.94 0.59 0.34 1.09 0.88 -0.09 0.93 0.82 0.62 0.97 0.86 1.05 1.41 0.40

z24 z64 0.00 -0.01 -0.08 -0.08 0.30 0.07 -0.08 =-0.3 -0.14 -0.28 -0.09 0.40 0.29 0.17 0.0 -0.03 -0.3 1 0.16 0.07 0.31 0.67 0.38 -0.11 0.42 0.37 0.55 0.43 0.39 0.47 0.37 0.28

z25 z63 0.00 -0.16 -0.15 -0.20 0.02 -0.09 -0.26 4 -0.1 1 -0.40 -0.26 0.12 0.29 0.19 -1.0 -0.49 -0.78 -0.20 -0.24 -0.03 0.74 0.55 -0.29 0.50 0.39 0.32 0.48 0.35 0.43 0.33 0.01

z26 z62 0.00 0.08 0.03 0.02 0.06 0.05 -0.06 -0.2 0.04 -0.03 0.00 -0.13 0.20 0.02 -0.9 -0.32 -0.48 -0.10 -0.21 -0.41 0.26 0.39 -0.11 0.44 0.28 0.28 0.42 0.35 0.30 0.25 0.16

191

Mono-

192

5

'H N M R in position 3 or 5:

Substituent

-H C -CH3 -CH2-phenyl -CH20H -CH2NH2 -CH2S-n-C3H7 -CH2S02-phenyl -CH=CH2 -CH=CH-COOH H -F a -C1 1 -Br 0 -OH -OCH3 -CN S -SCHz-phenyl -S-phenyl -SO3H 0 -CHO I t -COCH3 C -CO-phenyl / \ -COOCH3 -COO-n-CqHg -CSNH2 -CH=NOH

in position 4:

z32 z56 0.00 -0.02

z34

z35

z36

z54 0.00 -0.06

z53

0.00 -0.09

z52 0.00 -0.02

0.11 0.16

0.15 0.13

0.04 0.04

-0.04 0.00

-0.24

-0.15

-0.22

0.01

0.45 -0.01 0.20 0.20 -0.03

0.52 0.00 0.24 0.43 -0.37

0.34 0.14 0.19 0.34 0.15

0.17 -0.10 0.09 0.18 -0.24

-0.06 0.37 0.63

-0.49 0.50 0.72

0.02 0.06 0.43

-0.36 -0.16 0.50

0.70 0.45 0.72 0.47 0.62

1.14 0.42 0.68 0.54 0.60

0.81 0.12 0.30 0.37 0.23

0.70 0.20 0.37 0.34 0.34

0.68 0.39

0.67 0.43

0.24 0.19

0.26 0.15

z42 z46

z43 z45

0.00 0.01 0.00 0.07 0.01 -0.06 -0.09 0.12

0.00 -0.10 -0.15 0.14 0.03 -0.13 -0.18 0.13

-0.07 0.00 0.09

-0.03 0.05 0.35

0.02 -0.15 -0.05 0.46 -0.02 0.05

-0.29 -0.74 0.3 1 0.62 0.04 -0.16

0.47 0.40 0.36

0.58 0.58 0.40

0.34 0.35 0.24

0.54 0.68 0.37

5.6.2

Condensed Heteroaromatic Rings H Chemical Shifts of Condensed Heteroaromatic Rings (6in ppm relative to TMS, IJ( in Hz) 7.49 7.13d

a

7.52

7.19e \

f

7.42 7.55 6.99 d

@ 7.26 a

7.09 e \ f

Hs 10.1

7.40

7.83

@4:L'

7.36 d 7.34e \

f

7.88

7.41~

a 8.42

7.41d \ e 7.67 7.70

7.70

0

3Jab 2.5 5Ja,, 6Jad, 6Jae, 5Jaf: 0 4Jbc, 5Jbd, 6Jbe: 0 5Jbf 0.9 3Jcd 7.9

4Jce 1.2 5Jcf 0.8 3Jde 7.3 4Jdf 0.9 3Jef 8.4

3Jab 3.1 5Ja,, 6Jad, 6J,e, 5Jaf: 0 3Jag 2.5 4Jbc, 5Jbd, 6Jbe: 0 5Jbf 0.7 4Jbg 2.0 3Jcd 7.8

4Jce 1.2 5Jcf 0.9 5Jcg 0.8 3Jde 7.1 4Jdf 1.3 3Jef 8.1 6Jdg, 5Jeg, 4Jfg: 0

3Jab 5.5 5Jac, 6Jad, 6Jae,5Jaf:0 4Jbc, 5Jbd, 6Jbe: 0 5Jbf 0.8 3Jcd 8.0

OJaC -0.1 6Jad 0.4 5 -ae 1 n -.-n 3Jbc 8.2

4Jce 1.1 0.9 3Jde 7.2 4Jdf 1.0 3Jef 8.0

5Jc.

4J,e 1.2 3Jde 8.3

194

5 'H NMR

8.08

5Jab 0.1

7.50d \ e 8.14

6Jac -0.2 6Jad 0.4 5J,e 0.1 3Jbc 8.2

a

9.26

s

4Jbd 1.1 5Jbe 0.6 3Jcd 7.2 4Jce 1.1 3Jde 8.2

7.60

7.96

3Jab 9.2

LT')

9.06

H =11

d

Wa2' 7.25

6.50 e 6.31f \ N

b 6.64

/

a 7.14

7.76

N 8.34

3Jab 2.7 4Jac 1.2

5Jcg 1.0 3Jde 9.0 4Jdf 1.0 5Jdg 1.2 3Jef 6.4 4Jeg 1.0 3Jfg 6.8

5.6

a() 6.52

6*71

Heteroaromatics

5'77

0

c \

3Jab 7.9 4Jac 1.5 5 Jad 0.4 3Jbc 7.9

d

7.63 7.80

3Jab 9.8

3Jcd 8.5

4Jce 2.0 5Jcf 0.0

3Jde 8.6 4Jdf 1.8 3Jef 8.5

f 7.20

7.43d /

b 6.34

7.68e \ f 7.47

a 7.88

7.19 7 . 1 2 b u 1 )

6.42

c \

3Jab 6.1 3Jcd 8.0 4Jce 1.8 5JCf0.5

3Jde 7.0 4Jdf 1.1 3Jef 8.4

'Jab 7.8 4J,c 1.3 5Jad 1.1 3Jbc 7.1

d

7.68 8.00 7.43e /

\ b 7.26

7.61 f @a \

8.81

g

8.05

3Jab 4.3 4Jdf 4Jac 1.8 5Jdg 3Jbc 8.3 3Jef 5Jcg 0.8 4Jeg 3Jde 8.2 3Jfg

1.6 0.5 6.8 1.1 8.2

195

5 'H NMR

196

7.74

g

J

3Jab 6.0 4Jac 1.1 3Jbc 8.5

.

8.75 0 7.71 7.50

g

a

7.87 9.15

4J,b 5Jac 5Jad 3Jbc 5Jcg

0.8 0 ~0.5 6.0 0.8

3Jde 8.7 4Jdf 1.1 5Jdg 0.9 3Jef 7.0 4Jeg 1.3 3Jfg 8.2

8.77 7.57 7.73

f

8.30 7.84 9.29

3Jab 5Jbf 3Jcd 4Jce 5Jcf

5.7 3Jde 6.9 0.8 4Jdf 1.3 7.8 3Jef 8.6 1.5 0.8

4Jab 0 5Jbf 0.5 3Jcd 7.9 4Jce 1.2 5Jcf 0.8

;:;::$yJ f 8.01

8.07

f

'a 9.23

3Jab 3Jc-j 4J,e 5Jcf 3Jde

1.8 8.4 1.6 0.6 6.9

3Jde 6.9 4Jdf 1.2 3Jef 8.5

5.6 Heteroaromatics

7.93 9.44

f

a d 7.84

H

a

7.48

e

8.08

b7.49

5Jac 3Jcd 4Jce 5Jcf 3Jde

0.4 8.2 1.2 0.6 6.8

3Jab 8.5 4Jac 0.9 5Jad 0.6

3Jbc 7.3 4Jbd 1.3 3Jcd 7.6

5Jae 0.7 3Jbc 8.2 4Jbd 0.9 5Jbe 0.7

3Jcd 7.2 4Jce 1.2 3Jde 7.8

3Jab 9.0 4Jac 1.2 5Jad 0.6 5Ja, 0.9

3Jbc 6.6 4Jbd 1.4 3Jcd 8.2 4Jde 0.4

3Jab 8.4 4Jac 1.1 5Jad 0.5

3Jbc 7.1 4Jbd 1.8 3Jcd 8.0

5Jae 0.4 3Jbc 8.6 4Jt,d 1.0 5Jbe 0.4

3Jcd 7.0 4Jce 1.4 3Jde 8.2

a 10.3

9.09 d

y

7

./ 6b7.89 4 a 8.22

d 8.36

a 7.50

e

H

8.27

b7.57 a11.70

197

5.7

Halogen Compounds 5.7.1 Fluoro Compounds Fluorine in nature occurs 100% as 19F, which exhibits a s in quantum number I = 1/2. The signals of 'H atoms are split by coupling to F up to a distance of about four bonds.

B

IH Chemical Shifts and Coupling Constants of Fluoro Compounds (8in ppm relative to TMS,J in Hz) 4.10 CH3F 2JHF 46.4 1.24 b \/F

Ha'

a

4.36

2J,F 46.4 3 J b ~25.2 3J,b 6.9

\-p

4.37 H b 4.03 Hc

H,6.17

0.69

a

e Hd

4.32

5.45 CH2 5 2 1.7

J 50.2 ~ ~ ~ J , F57.3

6.25 CHF3 2

J 79.2 ~ ~

1.34

b y a F 6.1 3JbF F 3J,b 4.5 2009

2 J a ~84.7 3J,b 12.8 3Jb~ 20.1 3Jac 4.7 3 J c 52.4 ~ 2Jbc -3.2 3J,b 5.9 3Jac 2.4 2Jbc -6.7 3Jbd 10.8 3Jbe 7.7 3Jc, 12.0

1.57 H =

6

3

J 15.0 ~ ~

F

3 J , ~ 8.9 3J,b 8.4 4 J t , ~5.7 4J,c 1.1 de / b7.24 a 6.97 'J,F 0.2 'J,d 0.4 C 4J,c 2.7 7.03 3Jbc 7.5 4Jbd 1.8


199

5.7.2 Chloro Compounds l H Chemical Shifts and Coupling Constants of Chloro Compounds ( 6 in ppm relative to TMS,J in H z ) 3.06 CH3Cl

5.33 CH2C12

2.07

3.67 a/\/Cl

Y

c1E

9 3J 6*1

3J 6.4

1.55

1.33 \Cl

7.24 CHC13

3J 6.8

3J 7.2

3.47

1.81 m C 1 1.06 3.47

0.92 1.68 -Cl 1.41 3.42

1.60 5.39 Hc

Ha6.26

3Jab 14.5 3Jac 7.5 2Jbc -1.4

1.78 H-Cl

0.87 0 . 7 4 Hb :vl H i "a e Hd

F'

'Jab 7.0 3Jac 3.6 2Jbc -6.0 2.55 3Jbd 10.3 3Jbe 7.1 3Jc, 10.6

'::

3Jab 8.1 e o a 7 . 2 7 2.3 1.1 5Jad 0.5 d / b7.20 4 C

7.14

3Jbc 7.5 4Jbd 1.7

Hal

&::

d H 4 . 3 4

e 6 i/ 3 7b7'19 .81 C

7.17

3Jab 8.1 4Jac 1.1 4Jac 5Jad 0.5 2.4 3Jbc 7.5 4Jbd 1.4

5 ' H NMR

200 5.7.3

Bromo Compounds

H Chemical Shifts and Coupling Constants of Bromo Compounds ( 6 in p p m relative to TMS,J in Hz) 4.94 CH2Br2

2.69 CH~BI

2.47 \r?ig3J

6.4

3.63 B r w B r

Br 1.76

yBr Hal

5.97Hc

0.96 Hb 0.81 F y B r

3Jab 7.1 3Jac 3.8 *JbC -6.1 H H a 2.83 3Jbd 10.2 e Hd 3Jbe 7.0 3Jc, 10.5

e

d

a 7.43 / b7.15 C

3Jab 8.0 4Jac 1.1 5Jad 0.5 4J,c 2.2 3Jbc 7.4

1.66 \Br 3.37

6.82 CHBr3

1.89 b B r 1.06 3.35

1.73

7 4 % 2.33 HB -r

3Jab 14.9 3Jac 7.1 Ha 6.44 2jbC -1.9

&H

4.62


201

5.7.4

lodo Compounds I H Chemical Shifts and Coupling Constants of Zodo Compounds ( 6 in ppm relative to TMS, J in Hz)

2.16

3.90

CH3I

CH212

2.96

-

3J 7.0

3.70

1.95

6.57HhI

Y'

y:.24

1.88 \/I 3.16

1.88 11.03 3.16

1T-

y lI . 2 4

1.89

4.91 CHI3

0.93 1.80 11.42 3.20

% 1;:;;:

-

I: - I 2.06

Ha *JbC -1.5 6.53

6'23HC

Hal

0.76H

1.04 Hb

3Ja13 3Jac 2Jbc a 2.31 3Jbd

cy: H :

e Hd

de b / a 7 b7.03 . 6 4 C

7.25

7.5 4.4 -5.9 9.9 3Jbe 6.6 3Jc, 10.0

3Jab 7.9 4Jac 1.1 5Jad 0.5 4Ja, 1.9 3Jbc 7.5 4Jbd 1.8

8 & :

d H 4 . 7 2

202

5 'H NMR

5.8 Alcohols, Ethers, and Related Compounds 5.8.1 Alcohols

H Chemical Shifts and Coupling Constants of Alcohols

(6 in ppm relative to TMS, J in Hz) Aliphatic and alicyclic alcohols: 0.5-3.0 (in DMSO: 4-6) Phenols: 4.0-8.0 (in DMSO: 8-12)

0

Hydrogen bonds strongly deshield hydroxyl protons. The position of the signal may depend heavily on the experimental conditions. If a compound contains several kinds of hydroxyl protons (-OH, -COOH, H20), in general only one signal at an average position is observed because of rapid exchange. In dimethyl sulfoxide (DMSO) as solvent, this exchange in most cases is so slow that isolated signals are observed. In this case, the chemical shifts of hydroxyl protons are characteristic. However, if the sample contains strong acids or amine bases, the exchange rate increases, and also in DMSO, a signal at an average position is observed. Frequently, intermediate exchange rates lead to very broad signals extending over several ppm and, therefore, sometimes not discernible in routine spectra. As a consequence of fast intermolecular exchange of the hydroxyl protons, their coupling with the protons on the adjacent carbon atoms is usually not observed. However, in very pure (acid-free) solutions or in DMSO, the exchange is sufficiently slow so that the H-0-C-H couplings become visible. Their dependence on the conformation is analogous to that shown by the H-C-C-H couplings (Chapter 5.1). In case of fast rotation: 3 J = 5 Hz. ~ In cyclohexanols, ~ ~ the~ vicinal coupling constants for axial hydroxyl protons (3.0-4.2 Hz) are lower than those of equatorial ones (4.2-5.7 Hz). 3.39 3.9 CH30H, b

(in CDCl,)

in DMSO: 3J,b 5.2

1.18 2.61 liquid: in DMSO: 1.53 2.26 c\oHa 6, 5.27 6,4.5 -OH 6, 3.66 0.93 3.49 3.59 6, 1.19 (in CDCl3) (in CDcl3) ,Jab 4.8 ,JbC 6.9


1.16

2.16 3Jab 6.2 OH liquid:

(in CDCl3)

O H-H 2cJ=(

1.22

2.01 cl&OH 2.96 cl 4.15 (in CDC13) 60, in DMSO: 6.8

Y O H (in CDCl3)

6 , 1.23

203

(a2

5.2

5.6 CH-OH

(in DMSO)

(in DMSO)

(in DMSO)

3.40 For derivatives inDMSO:

For derivatives

0

4.0-4.5 3Ja,0H 4.2-5.7

1.45

6.82 4Jbd 1.7 (in CC14) * in DMSO: 6 0 ~ 9 . 3

1.17

NO2

(in DMSO)

7.00 (in CDCl3)

5 'H

204

NMR

I H Chemical Shifts of Enols ( 6 in ppm relative to TMS,J in H z )

=16

-16 3Jab 9.7 3Jbc =8

5.04

3Jab5.1

Q

Ha CH3 7.90 H b 2.11 5.60

2.00

0

(in CDC13, partly enolized)

5.8.2

Ethers H Chemical Shifts and Coupling Constants of Ethers

(6 in ppm relative to TMS,J in Hz) 3.21

2Jgem -10.6

f i 0%

\ 0/

3.27 0.93

3.37

*y)-

b 3J& 1.15

1.55

3.40 1.38

*,O

1.54 0.92

3.16 Hb6.44 Hc 3.88 a\o+ Hd 4.03 (in TMS)

0.3 7.0 3Jbd 14.1 2Jcd -2.0

4Jab 3Jbc

.

V.

3.74

a&o'

1.27

6

A

1.24

7.0 0.4 3Jcd 6.9 3Jce 14.4 2Jde -1.9 3Jab

Hd 3.96 4Jbc

Y He 4.17

H Chemical Shifts and Coupling Constants of Cyclic Ethers

( 6 in ppm relative to TMS,J in Hz)

A

2.54

In derivatives: 2Jgem 5 - 6 3Jcis 4.5 3~trans3.1 Throughout: Jcis > Jtrans


e a 4.73

c

b 2.72

31Jlac

c

8*3 Jab,trans 0.7 3Jbc 2.5

b

4.82 2.53

0;65; c

1.98

c

7.56

d

0

a 4.63 3Jab

4J

-2.5 ad,& 7.1 4Jad,trans 4*6 3Jbc 6.3

b 5.89 4JaC

c

2.6 2.6

4Jbd 3Jcd

6.38

1.59

6.6 aa,anti

5.9.5 Nitriles and Isonitriles I H Chemical Shifts and Coupling Constants of Nitriles (6 in ppm relative to TMS, J in Hz)

1.98 CH3CN

1.31

bCN J,ic 7.6 2.35

2.29

0.96 1.63 -CN 1.50 2.34

?v

6.07 5.73 3Jab11.8 0.94 3Jab 8.4 H h H a 3Jac 17.9 0*93 Hb 3Jac 5 * 1 2Jbc 0.9 2Jbc -4.7 Hc CN H i 'Ha 3Jbd 9.2 6.20 e 1.36 3Jbe 7 * 1 3Jc, 9.5

3Jab

a

C

1.11

1.35

7.0 7.4 4Jac -0.05

1.71 b -CN3Jbc

1.37

e6

YCN 3Jab 7.8

a 7.51 4Jac 1.3

\

5Jad 0.7 7'44 4Ja, 1.8

C

7.56

3Jbc 7.7 4Jbd 1.3

IH Chemical Shifts and Coupling Constants of Isonitriles (6 in ppm relative to TMS, J in Hz) Because of the symmetrical electron distribution around the N atom, the quadrupole relaxation of the nitrogen nucleus is so slow that the 14N-lH coupling becomes observable and leads to triplets with relative intensities of 1:l:l (spin quantum number of 14N: I = 1; natural abundance, 99.6 %): b a -C-C-"NC H2 H2

l J l a 1.8-2.8 lJlbN 1.5-3.5


2.85

2JaN 2.3

CH3NC a

3Ja1, 7.3 2 J , ~2.0 3 J b ~2.4

1.28 b\NC a

21 3

1.45 b y N C a 3'87 3 J b ~2.6

$:

i::

3.89

5.9.6

Cyanates, Isocyanates, Thiocyanates, and lsothiocyanates H Chemical Shifts and Coupling Constants of Cyanates, Isocyanates, Thiocyanates, and Zsothiocyanates ( 6 in ppm relative to TMS,J in Hz) 1.45 \OCN 4.54

3.02 CH3NCO

1.63 f i NCO 0.99 3.26

1.29

2.61 CH3SCN

1.52 2.98

3.37 CH3NCS

'c NCS 3.64

1.20 \NCO 3.37 4.77 6.12 3Jab 7.6 3Jac 15.2 'WHa 2Jbc -0.1 Hc NCO 5.01

N

5 'H NMR

214

5.1 0

Sulfur-Containing Functional Groups 5.10.1 Thiols

1H Chemical Shifts and Coupling Constan (6 in ppm relative to TMS,J in Hz)

I

f Thiols

Typical ranges of SH chemical shifts: &-SH

1-2

O

S

H 2-4

The exchange with other SH, OH, NH, or COOH protons is generally so slow that the chemical shift is characteristic and the vicinal coupling with SH protons becomes visible (5-9 Hz in aliphatic systems with fast rotation). 2.00 1.26 CH3SH b

3Ja1, 7.4

a

(in benzene)

1.31 1.39 V S H 2.44

1.63 1.33 -SH 0.99 2.50 3Ja1, 5.7

0.92 1.59 1.32 -SH 1.43 2.52

S

1.43

H

YSH

S

1.88 1*35 d H 2.68

1.2 0.6 4Ja, 2.1 3Jbc 7.5 4J,c 'Jad

C

7.04

5.10 Sulfur-Containing Functional Groups

215

5.10.2 Sulfides

I H Chemical Shifts and Coupling Constants of Sulfides (6 in ppm relative to TMS, J in Hz)

2.12

‘S/

2.10 2.51 \S1.26

2.09 2.49 1.42 ‘S1.56 0.92

2.43 0.98 & - . S V 1.59

/I(1.39

&,S

a k s

k 9 3 1.25

a 6.35 3Jab 10.3 H b 5.08 3Jac 16.4 \ 2Jbc -0.3 , H c 4.84 (in TMS)

2a12 q

\s

7.16 7.02 7.20 I H Chemical Shifts and Coupling Constants of Cyclic Sulfides ( 6 in ppm relative to TMS, J in Hz)

2Jgem 0 L1 2*27 3Jcis 7.2 3 ~ t r a n s5.7 S

S c ()a b

2.94

3.21 2Ja,gem -8-7 2Jb,gem -11.7 8.9 6.3 4~ac,cis 1.2 ‘~ac,trans -0.2 3Jab,cis 3Jab,trans

0 2 . 7 5 1.88

S

5

216

'H NMR

5 . 1 0.3 Disulfides and Sulfonium Salts

H Chemical Shifts and Coupling Constants of Disulfides and Sulfonium Salts ( 6 in ppm relative to TMS,J in Hz) 2.30

2.67 &+/\ 1.35

,&As/

0

e

&/S'S-/

:::: l::

7.50 7.28

2.63 1.03 1.71

0 2 . 7 1.9

4Jae 0.5 5Jad 2.0

d

*/s\

2.94 \

-s+ /

,

1-

3Jbc 7.2

5.10.4 Sulfoxides and Sulfones I H Chemical Shifts and Coupling Constants of Sulfoxides and Sulfones (6 in ppm relative to TMS,J in Hz)

qs00 / \

2.84

+'

/u 0 '

1.47

2.80 2.94

3Jbc 10.0 3Jbd 16.5

2'96

b6.14 2Jcd -0.5 Hb6.76

qSQo 1.41 2.85 ' x 1 3

% eo

1.44

ysy

%go O=

- 3.06

Q63t

7.94 7.61 7.65


21 7

5.10.5 Sulfonic, Sulfinic, Sulfurous, and Sulfuric Acids and Derivatives

H Chemical Shifts and Coupling Constants of Sulfonic, Sulfinic, Sulfurous, and Sulfuric Acids and Derivatives ( 6 in ppm relative to TMS, J in H z ) 11-12 alk-SOz-OH

3.0

2.5

-/3.7(

3J,b 4Jac 5J,d, 7.94 4Ja, e \ a 7. , / hb e-l o/ a 77.60 3Jbc d C 4Jbd 7.62

2.68 ,cH3

8.0 1.2 0.6 2.0 7.6 1.4

3.6

J,, c

7.60

4Jbd 1.3

6 sJH2

7.37

7.85 / 7.58 7.58

5 . 1 0.6 Thiocarboxylate Derivatives

H Chemical Shifts of Thiocarboxylic Acids and Derivatives

(6 in ppm relative to TMS, I JI in Hz)

3J,b 5.9 2.41S H' 2.30

5.09

s/

a 6*47 4J,c 2.0

7.84 2.27

2.2

3Jbc 2*8

6.4

5 'H NMR

218

5.1 1

Carbonyl Compounds 5.1 1.1 Aldehydes

' H Chemica Shifts and Coupling Constants of ..,.#ehyi es (6 in ppm relative to TMS,J in Hz) Typical ranges for chemical shifts and coupling constants of aldehyde protons: alk-CHO 9.0-10.1

O

C

H

3J,ic 0-3

alken--CHO 9.0-10.1

cHO

O 9.5-10.5

R 9.60 CH2=O 'IJIgem 42.4

1.67

9.74

6.26

C=X

6.26

H=i="

Hd 6.11

0

ycfo

1.13 3Jab 2.0

0.97 2.42

2.20 9.80 b a C H r C H O 3Jab 3.0

9.57

3Jab 1.1

2.39

3jVic

10.2-10.5 m , p : 9.5-10.2 0:

1.13 9*79 +CHO 2.46

1.07

Z8

8

3Jab 1.4

9*48

YCHO

3Ja1, ~ 8 . 0 4Jac ~ 0 . 3 4Jad 10.1

Ha 9.51 7.61

4Jce 1.3

5.1 1 Carbonyl Compounds

219

5.1 1.2

Ketones I H Chemical Shifts and Coupling Constants of Ketones ( 6 in ppm relative to TMS, J in Hz)

%:

k . 0 5 a J 1 4 & 4Jab 0.5 2.14 2.14 2.47 1.98 2.32 0.85

2.09

(in benzene) in CDC13: c 1.56 d 0.93

6.27

5.90

6.30

6.67

2.55 7.45

2.92

2.86 1.02

7.44

3.58 d

ae 1.8 3Jbc 7.5 4Jbd 1.3 '='

5 'H NMR

220 7.74

Qni

? I

7*57

2.68 7.47

?!

fs

7.46*

( J

2.63

6-78

.--

II

7.21 2.93

j.13

*

0

assignment uncertain

I H Chemical Shifts of Diketones ( 6 in ppm relative to TMS)

2.34

3.62

2.17

For the enol form, see Chapter 5.8.1 Long-Range Coupling in Ketones (IJI in Hz) Coupling over the C=O group is often detectable for fixed conformations in Warrangement of the coupling path:

Br

5.1 1.3 Carboxylic Acids and Carboxylates

' x A

I H Chemical Shifts of Carboxyl Protons ( 6 in ppm relative to TMS, J in Hz) The position of the COOH signal depends on the solvent, the concentration, and the presence of other exchangeable protons. Intermediate rates of exchange with other protons may induce very broad lines, which are sometimes not even detected. 8.06

11.0 H-COOH

2.10 11.42 CH3-COOH

11.73 1.16 vCOOH 2.36

1.06

VCOONa 2.18

(in D20)

1.68 11.51 m C O O H 1.00 2.31

1.23

1.21

0.93 1.62 -COOH

11.88

11.96

1.39 2.35

11.19 COOH

11.49

y'"""

3.45

12.2 COOH

Coo,

(

COOH

2*43

(in DMSO)

OOH-12.5 3Jab 7.9 3Jab 10.5

5.95 Ha 6.15

OH12.8 3Jac 17'2 2Jbc 1.8 C

3Jbc 7.5 4Jbd 1.3

7.60

5.1 1.4

Esters and Lactones H Chemical Shifts and Coupling Constants of Aliphatic Carboxylic Acid Esters ( 6 in ppm relative to TMS, J in H z )

,f,o,:z b

41Jlab 0.8

l o q ! c 4 . 6 9 Ha 8.03 Hd 5.01

Ha 8.07

4Jab -0.7 3Jbc 6.4 5J,c 1.6 3Jbd13.9 5.Jad 0.8 2Jcd -1.7

c=x &67 2.01

2.04

1.26

2.05

1.65

4.06 1.39 2.02

1.23

2.04

0-

1.60

0.94

J O k 1.45

5 'H NMR

222

C

7.07

0.98

2.32

0

.

9

l*?Q7 2.56

2.22

w $66

1.33 2.31

For esters of boronic, nitric, and sulfuric acid, see Chapter 5.12. I H Chemical Shifts and Coupling Constants of Alkyl Esters (6 in ppm relative to TMS)

qoT40

5

F

4 b

y

Hc 0 6.40

%

3Jab 10.6 3Jac 17.4 2Jbc 1.5

do% 1.30

3.76

nK22 .37 1.77

I.4U

C

7.46

7.37


223

H Chemical Shifts and Coupling Constants of Lactones

(6 in ppm relative to TMS, J in H z )

&C

3.56 4.29

4.28

2Jab -17.5 Ha 2.41 3J,, 9.5 3Jad 6.9 4J,, 0.3 Hf Hd 2.23 4jaf -0.5

*J,d -12.7 3Jce 7.9 3Jcf 6.3 2Jef -8.8

5 . 1 1.5 Amides and Lactams

Amide Protons ( 6 i n ppm relative to TMS, J in Hz)

1

R

"2

5-7

R: alk, ar

1

R N H 6-8.5

R: alk, ar

1 /o R N H

R: alk, ar

7.5-9.5

Line Widths The signals of the NH protons are often broad because the 14N-lH coupling is only partly eliminated by the quadrupole relaxation of 14N (spin quantum number, I = 1; ~ J N H = 60). In primary amides, the hindered rotation around the CO-N bond is another reason for line broadening. At slow rotation, the chemical shifts of the two primary amide protons differ by about 0.5-1 ppm. Vicinal Coupling H- C-N-H Due to the slow intermolecular exchange of amide protons, their coupling to neighboring hydrogen atoms is usually detectable. The splitting of the C-H signal is clearly observed even in those cases where the signal of the NH proton is broad and featureless. The H-C-N-H coupling depends on the conformation in a similar way as the H-C-C-H coupling (see Chapter 5.1). For N-CH3 and N-CH2 groups: 3 J sz 7. ~ ~ ~ ~

C =X

5 'H NMR

224

Tertiary Alkylamides The rotation around the CO-N bond is usually so slow that, with different Nsubstituents, two separate signals are observed for the two conformers. In general, the following relationships hold: for NCH3, NCH2CH3, and NCH(CH3)2 for NCH(CH& and NC(CH3)3 for NCH,

Gcis to 0 5 Gwans to 0 &ram to o 5 %is to o %is to o Gtrans to o

-

Formamides ( 6 in ppm relative to TMS, IJI in Hz) In the more stable conformer of monosubstituted formamides, the substituent occupies the cis position relative to the carbonyl oxygen. In the more stable conformer of asymmetrically disubstituted formamides, the larger substituent occupies the trans position relative to the carbonyl oxygen.

H

- '*' ii' H

,kN/2*:8

8.1

H7.9 90 %

Ha 8.02

'

Ha

"7.9

2.88 = 10%

8.2-8.7

N

B

R

7.5-9.5

1 2.71

4J,b -0.3

4Ja, -0.7

b 2.97

A 1 2 2.83

1.19

= 30 %

= 70 %

Acetamides ( 6 in ppm relative to TMS,J in Hz) In monosubstituted acetamides, the substituent of the only observable conformer ; ; -. X is cis to the carbonyl oxygen. In disubstituted acetamides, the more stable conformer has the larger substituent cis to the carbonyl oxygen.

0

3.26

3J,b 4.8

1.98

Hb 6.4

1.98

H b 1.14 6.7

3Jab 5.9

AN)96 -2.0

H

1.55


225

3.21 1.35 3Jab 8.4

~ 2 . 0 H b 1.13 8.1

1.98

4 '

2.08

.

N H 1.49 0.92 7.05

=2.O

-

N/ 3.02 5Jab 0.1 5Jac 0.5 2.94

A N L y 2

I 2.83

1.15

= 60 %

= 40 %

JNb;::: L

-2.1

H

a

7.64

1.03

0

f N/2'70 l 2

3Jab 8.2 4Jac 1.2 5Jad 0.5 4Jae 2.4

H 1.28 7.3

3.36

3.46 1.97

l H Chemical Shifts of Lactams ( 6 in ppm relative to TMS)

C=X

0

5.1 1 . 6 Miscellaneous Carbonyl Derivatives H Chemical Shifts of Carboxylic Acid Halides (6 in ppm relative to TMS, J in Hz)

A

2.66

DF

3Jab 10.7 3Ja, 17.3 2Jbc 0.8

2.82 A B ,

6.25 Ha

6.14

6.16

3Jab 10.6

3Jab 8.0

3Jac 17.4 2Jbc 0.2

1.2 8.07 5Jad o-6 7.47 4 ~ a e 2.0 3Jbc 7.5 4Jbd 1.4

k, 6.35

4Jac

de&;

C

7.63

H Chemical Shifts of Carboxylic Acid Anhydrides

(6 in ppm relative to TMS)


227

H Chemical Shifts of Carboxylic Acid Imides

( 6 in ppm relative to TMS)

0

2.62 2.06

3.83

2.50

l H Chemical Shifts of Carbonic Acid Derivatives ( 6 in ppm relative to TMS)

4.13 1.2-1.7

o+O- 0- 3.8 1.2-1.7 0.93

3.94

5.5

[>s

2.78 \ l N H 5.16

o z 1.23

c=x

5 'H NMR

228

5.1 2

Miscellaneous Compounds 5.12.1 Silicon Compounds I H Chemical Shifts and Coupling Constants of Silanes and Silanols ( 6 in ppm relative to TMS, J in H z )

a R-?i-H R

For R: H, SiX3: 2-4 2-6 other: 3-6

H a 3.20 H-Ai-H I

H 'J,si -202.5

b

FH3 0.19 'Jasi-202.5 I t y i - H 3.58 35 4 7 a ab . H

0.42

0.79

YH3

CH3-g iC1 CH3 5.88

6.11

'Jasi -150 to -380 (4.7% natural abundance of 29Si, "Si satellites")

Cl-

YH3

i C1

I$-

CH3

3 'aD 1. ldh 3Jac 20.2 2Jbc 3.8

1.14 YH3

Cl-7x1 c1

I-."

4Ja, 5Jad 3Ja, 3Jbc 4Jbd

1.4 0.7 1.4 7.5 1.2

5.1 2 Miscellaneous Compounds

229

The silanol hydrogen is exchangeable with D20. Slow intermolecular exchange is observed in dimethyl sulfoxide as solvent so that the vicinal coupling in H-Si-OH is detectable.

(in DMSO)

5.1 2 . 2 Phosphorus Compounds H Chemical Shifts and Coupling Constants of Phosphines and Phosphonium Compounds ( 6 in p p m relative to TMS, IJI in Hz) 1.79 a

PH3

lJap 184.9

0.98 2.63 lJap 186.4 b a 2Jbp 4.1

CH3-PH2

3Jab

8.2

1-06 'Jap 191.6 2Jbp 3.6 H 3Jab 7.7

CH3\p/CH3 a

3.13

I H Chemical Shifts and Coupling Constants of Phosphine Oxides and Sulfides ( 6 in ppm relative to TMS, IJI in H z )

5 'H NMR

230

H 6.60

2Jap 13.5 3Jbc 11.8 2Jbp 25.9 3Jbd 17.9 Hc6.14 3Jcp 45.3 2Jcd 1.8 3Jdp 25.4

"$k

6.26

\

Ha6.82 2Jap 24.9 H b 3Jbp 47.0 6.17 3Jcp 25.5 3Jab 11.7 6*34 3Jac 17.9 2Jbc 1.6

H Chemical Shifts and Coupling Constants of Phosphonous Acid Derivatives ( 6 in ppm relative to TMS, IJI in H z ) c 1.20 2Jap 9.7 y q r y 4 . 2 0 a 1.10

3JbP 9*5 4Jcp 6.0

\N\

q ' xa 3.49 \/sr,9' bl .25 /o 3Jap 10.8

-0

a 3.85

f

2Jap 8.7 8.0 4Jcp ~ 1 . 0 3Jbc 7.0

fvc 1.01 3Jbp "

b 2.96 a 1.18 (in CCl4) 3 J a ~ 8.0

4Jbp 0.6 3Ja1, 7.1

Ia

I "\Q"' /

N\

3Jap 8.9

2.43

5.12 Miscellaneous Compounds

231

IH Chemical Shifts and Coupling Constants of Phosphonic and Phosphoric Acid Derivatives (6 in ppm relative to TMS, J in Hz) 3.66 O’b a -$=O 1.43 I 0,

3.78 a

\oI

&’

3.65 2JaP-18.O 7.40 7.72 1.72 OI G 3Jbp 19.5 2JaP 17*3 a p d = O 3Jcp 10.0 \ 3Jbp 11.o 3J,b 7.5 7’48 d e b \ 1.06

-o-P=o

1.29

4.04

1.28

3J,p 13.3 4Jbp 4.1 h=o 5Jcp 1.2 3Jab

4Jac 5Jad 4J,, 3Jbc 4Jbd

7.7 1.4 0.6 1.6 7.6 1.4

4.06

b a -0

9I

Lo+o

J,p 11.0

b

I H Chemical Shifts and Coupling Constants of Phosphorus Ylids (6 in ppm relative to TMS, J in H z )

2Jab 12.7 2J,c -1.2

Misc.

5 'H NMR

232

5.12.3 Miscellaneous Compounds

H Chemical Shifts and Coupling Constants of Miscellaneous Compounds ( S i n ppm relative to TMS)

Li- CH3 -1.32(in benzene) -1.74(in ether)

0-

,o-i

3.5

0-

6.80 (in DMSO)

o."-o+

4.78

e\ / 4.2 N-0 d'

1.39

0.71

R / 4*3 o=c1-0 II

0

6.67

H, 5.51

MnBr

6.19

6.70

3~~~17.7 3J,c 23.3 2Jbc 7.6

3Jab 12.2

3Jac 19.8

FH3

CHrTb-CH3 CH3 (in DMSO)

6.15

2Jbc 2.1

0.72

7.40 7.44

0.4

7.24

5.13 Natural Products

233

5.1 3 Natural Products 5.13.1

Amino Acids I H Chemical Shifts and Coupling Constants of Amino Acids ( 6 i n ppm relative to TMS; J in Hz, solvent: tripuoroacetic acid (TFA) or D20)[ 11

7.47 4.28 a b

3.58 'H3N)K0-

3Jab 5.7

0

0

(in D20)

(in TFA)

?(.-

1.86

d 1-25 3Jab 5.7

1.49

+H3Nf 3.79

4.49 O

(in TFA)

7.i3

'H3N b 4.32 0 (in TFA)

(in D20)

g

a c,d4: 7.38 'H3N b 4.28 0 (in TFA)

3Ja1, 5.5 f 1.10 3Jbc =6.7 3Jeg ~6.1 3Jbd 6.7 5.7

4.51 3Jab 6 4.0* OH 3Jbd 4.0" 2J,d -13.5

c'd 4.56 3Jbc

a 4.650 7.70 (in TFA)

3Jef

* average value

3Jbc 4.2 OH 3Jcd 6*9

1.10

3Jab

5.5

1.21 d

a 4.410 7.35 (in TFA)

d1.67 3J,b 5.5 4.82 3Jbc 4.5 7.63aH0&oH 'H3N b 3Jcd 6.5 C

4.44 0 (in TFA)

Nat ?Ir ;i I Products

e

a 4.680 7.58 (in TFA) * average value

3Jab 5.3 3Jbc 5.0* 3Jbd 5.0" 2Jcd -15.5 3Jce 9.1* 3Jde 9.1"

f

a

7.73

2.27'Jab

5.5

4.670

(in TFA)

* average value

z7.45

7.03

p

7.27

7.3 0 =7'45 3Jbc 8.5 3Jbd 4.5 2Jcd -14.5 3.64 cd 3.37 7.4 a

+H3N*OH a 4.68 0 7.33 (in TFA)

7.73

OH

OH

6

4.64 (in TFA)

3Jab 5.1 3Jbc 4.7

2 2.63 . 5d. 4 7.71 a

4.76 0 (in TFA)

3Jab 5.8 3Jbc 5.6* 3Jbd 5.6" f 2.00 2Jcd -15.0 ~ 1 . 8 3Jce 6.0* 2.35 d 3Jde 6.0" OH 3Jfg ~ 6 . 0 3Jgh e6.0 4.52 0 h

r!rirl ! i R I til

l,Jt!;'lS

6.97

(in TFA) * average value

+H3N b

OH 3Jab 5.5 3-01 ::bcbd 5.6* OH

4.60 0

2Jcd -15.5 3Jce 6.2* 3Jde 6.2*

(in TFA) * average value i 6.19

i 6.19

3Jab 5.5 3Jbc 5.3* 3Jbd 5.3* 2Jcd z-15.0 3Jce =6* 3Jcf =6* 3Jde =6* 3Jdf r6* 3Jeg 6.5" 3Jfg 6.5* 'Jgh 5.3

+HzIY"2 4.46 0 (in TFA) * average value

5.1 3 Natural Products

2.06 d 2.04 e

I

b2.42 c 2.14

4.33 (in D20, pH 2.0)

1.07 d 1.05 e

-

b 1.45 c

1.04

2.81 (in D20, pH 13.0)

a

1.63 d 1.60 e

3Ja1, 8.5 3Jac 6.5 2Jbc -13.5 3Jbd 7.5 3Jbe 5.5 4Jbf -0.4 4Jbg 0.0 3Jcd 5.5 3Jce 7.5 2Jde -13.0 3Jdf 5.5 3Jdg 7.5 3Jef 7.5 3Jeg 5.5 2Jfg -11.0

7.205

H (in TFA)

OH

3.9* e

3'9*f H2'\ 0 8.60 g 4 8.00 h (in TFA)

3Jab 8.4 3Jac 6.2 2Jbc -13.5 3Jbd 7.6 3Jbe 5.4 4Jbf -0.4 4Jbg 0.0 3Jcd 5.6 3Jce 7.8 2Jde -13.0 3Jdf 5.7 3Jdg 7.9 3Jef 7.9 3J,g 5.7 2Jfg -11.0 3Jab 8.2 3Jac 10.4 2Jbc -15.0 3Jbd 4 at ~ 7 2 0 ; for n c 4 at higher wavenumbers; in cyclohexanes at 4 9 0 , weaker Beyond n o m 1 range: 1060-800 Cycloalkanes, numerous bands, unreliable 2200-2080

In general, substitution of L by isotope L':

\ /

/

C\

6 IR

248

6.2 Alkenes

c;,:..-c 6.2.1 Monoenes

c=cst

t

C=C-H 6 OOP

Typical Ranges (v in c m - l ) Assignment = C H 2 st

Range 3095-3075

=CH st

3040-3010

Comments Medium, often multiple bands

Medium, often multiple bands CH st in aromatics and three-membered rings fall in the same range In cyclic compounds: ~3075

D

-3020

0

=CH 6 ip

1420-1290

=CH 6

1005-675 A number of bands In the same range also: ar CH 6 oop, C-0-C 'y, and C-N-C y in saturated heterocyclics, OH 6 oop in carboxylic acids, NH 'y, NO st, SO St, CH2 y, CF st, CCl st

OOP

Of no practical significance

6.2 Alkenes

Assignment Subranges:

Range

Comments

c=c CH=CH2

C=CH2

249

C=C-C=O 1005-985 ~980 920-900 =960 (with overtone -810 at 1850-1800) 900-880 -940 (with overtone 4 1 0 at 1850-1780) 990-960 -975

C=C-OR =960 415

C=C-O-C=O 2950 470

=795 -960

-950

H%H "H

HH c=c s t

725475

-820

840-800

-820

1690-1635 Subranges: 1650-1635 1660-1 640 1690-1665

Of variable intensity, weak for highly symmetric compounds, strong for N-C=C and O-C=C CH=CH2 C=CH2

%H

H

Weak

1665-1635

'HH

1690-1660

HH

1690-1650

Weak, often absent

Weak, often absent

Beyond noma1 range: down to C=C-X with X: 0, N, S ; of higher intensity; in vinyl ethers often doublet due to rotational 1590 isomers

-

c=c

6 IR

250

At lowerfrequency if conjugated with: c=c =1650 ~1600 czc =1600 CzN

~1620

c=o

~1630

4

~1630

4

=1640

Examples (v in crn-I) 1645 994 912

=L

\ g'76:

1575 826 76 1

c1

liquid: CC14: 1610 1634 1608 987 964 810 943

7

1

< cI=/Cl

/ 0-

1663

1647 889 669

1682 972 963

1650 709

1667 825

1595 848 714

1587 929 835 780

E 958 793

1670 1652 937 925

1660

1673

-Ido

1663

3O 7

=\

1650

6.2 Alkenes

w-N-

1640

1662

1652 1612

1830 1621 987 818

251

/

N-C=C-CrN CEN-

2150-21 10

Strong

WGN-

N

6 IR

276

Assignment -NkN

Range Comments Medium, frequency depends on anion 23 10-2130 In the same range: C=C st, X=Y=Z st as, NH+ st, PH st, POH st, SiH st, BH st

Examples (v in c m - l ) 2222

N b C N

2273

NC

CN

NC

CN

2257 2222

)=(

NaCN, KCN 2080-2070

wcN 2252

-CN

2235

NC-CN

2235

NC+CN

2252

2245

CN

2220

CN

Q AgCN

&OH

2178

NH2-CN

2268

6.9.6 Diazo Compounds

r\i Assignment N k N st

Range 23 10-2130

C=N+=N-

2050-2010 Very strong Subranges: 2050-2035 R-CH=N+=N- R: a1 or ar 2035-2010 R+=N+=N- R: al or ar Beyond n o m 1 range: 2 100-2050 R-CO-C=N+=NC=O st ~ 1 6 4 (R: 5 al) C=O st ~ 1 6 1 (R: 5 ar) C=N+=N- st sy: -1350, strong 2180-20 10

Comments Medium, frequency depends on anion

O e-% N -

C=O St 1655-1560


277

6.9.7 Cyanates and Isocyanates

Cy an a tes

I

t

3600

2800

2000

1600

1200

800

400

1600

1200

800

400

Isocyanates

3600

Typical Ranges

-N=C=O st as 2800 2000

(V

I

in crn-l)

Assignment

Range

Comments

OC=N st

2260-2 130

Medium to strong

2220-21 30

(WEN)(OCEN)~ st SY

1335-1290

c-0 st 1200-1080 N=C=O st as 2280-2230 ~2300

Strong Strong,sharp -CF2NCO

N=C=O st sy 1450-1380 Weak Beyond n o m 1 range: 2220-21 30 (N=C=O)-

N

6 IR

278

Examples (v in crn-l) CH3NCO

\NCO

2265

2280

YNCO

2270

bNCO

2256 (1629 C=C)

li

2246

NCO

6

O

2267

6.9.8 Thiocyanates and lsothiocyanates

Thiocyanates

I

I

3600

2800

2000

1600

1200

800

400

N Zsothiocyanates %T C-N

st

-N=C=S

st SY

-N=C=S st as 1

I

3600

2800

2600

1600

1200

800

400


Typical Ranges Assignment S C = N st

c-s

(v

279

in crn-l)

Range 2 170-2 130 2090-2020

Comments Medium, sharp (SC=N)'

750-550 N=C=S st as 2200-2050

Often doublet Very strong, generally doublet, Fermi resonance

st

N=C=S s t sy 950-650 =950 a1 -N=C=S 700-650 -N=C=S Beyond n o m 1 range: 2090-2020 (N=C=S)-

C-N s t

1090-1075

Examples (v in crn-l) CH3NCS

neat: 2206 21 14

uNCS

2105

in CCl,: 2221 2106 2077

eNCS

/\rNCS

2062

6s

2173 2097 2068

neat: 2090 in CCl,: 2065 in CHC13: 21 12

N

6 IR

280

6.1 0

Sulfur-Containing Functional Groups 6.10.1 Thiols and Sulfides

I

I

3600

2800

2000

1600

1200

800

400

Typical Ranges ( v in c m - l ) Assignment S-H st S-H 6

c-s s-s Also:

st

st

Range 2600-2540 915-800 710-570 400 ~2880

~2860 =1430 1330-1290 ~1425 815-755 =630 725-550

S

Comments Often weak, narrow Weak, of no practical significance Weak, broad, of no practical significance Weak, of no practical significance (S-)CH3 st as (S-)CH2 st as (S-)CH3 6 as (S-)CH3 6 SY (S-)CH2 6 S-F st, strong S-N st in S-N=O S-C in S-CsN, often doublet

Examples ( v in cm-l) -SH

2950

\S,s/\

698 668 64 1

Hs/\/’SH

2525

566

esH 2585

662


28 1

6.1 0.2 Sulfoxides and Sulfones

Sulfones

I

I

3600

Typical Ranges Assignment

s=o st

2800

(V

2000

1600

1200

800

400

in c m - l )

Range 1225-980 Subranges: 1060-10 15 =1100

Comments Strong, sometimes multiple bands R-SO-R R-SO-OH

e1135 1225-1 195 ~1135 ~ 1 0 3 0~, 9 8 0 ~ 1 1 0 0=lo50 ,

R-SO-OR RO-SO-OR R-SO-C1 R-SO2RSO

S-0 st 870-810 OH st free ~ 3 7 0 0 , H-bonded ~ 2 9 0 0~, 2 5 0 0 S-0 st 740-720,710-690

N=SO: ~ 1 2 5 0~, 1 1 3 5

S

6 IR

282

Assignment

‘go /

st as 0 st sy

Range 1420-1000

Subranges: 1370-1290, 1170-1 110 1375-1350, 1185-1 165 ~1340,~ 1 1 5 0 1415-1 390, 1200-1 185 1365-13 15, 1180-1150

s-0 S

st

Comments Very strong

R-S02-R R-S 02-OR

R-S 02-SR RO-S02-OR R-S02-N N-H St: 3330-3250; N-H 6: ~1570; S-N st: 910-900

1410-1375, 1205-1 170 1355-1340, 1165-1 150

R-SO2-hal

1250-1 140, 1070-1030 1315-1 220, 1140-1050

R-SO3-

870-690

Of variable intensity, weak in sulfites

R-SO2-OH

0-H st, H-bonded: =2900, ~2400 hydrated: 2800-1650, broad

RO-SO~-


283

6.1 0.3 Thiocarbonyl Derivatives

S-H st

1 3600

2800

2000

1600

1200

8bO

4bO

Typical Ranges ( v in crn-l) Assignment

Range

c=s s t

1275-1030 Subranges: 1075-1030 1210-1080 -1215

Comments Strong, narrow Thioketones Thioesters Dithioacids

1125-1075

Thioacid fluoride

1100-1065

Thioacid chloride

1140-1090

Thioamides and thiolactams P=S st

SH st: ~2550 SH 6: =860 perfluorinated: 1130-1 105 perchlorinated:

1 loa-1075

Also:

750-580

C-N st: 1535-1520 NH 6: 1380-1300

S 6.1 0.4 Thiocarbonic Acid Derivatives

Trithiocarbonates

c=sst I

3600

2800

2000

1600

1200

800

400

6 IR

284

Xu n t h a tes

%T

V S-H st COC st sy 3600

2800

2dOO

1600

I

1200

800

I

400

Thiocarbonates

%T c=sst

I

3600

2800

6

2000

1600

1200

800

I

400

c=sst

% T

,

Typical Ranges ( v in crn-l) Assignment S-H st

c=s st

COC st as COC st sy

Range 2560-2510 2600-2500 1100-1020 1070- 1000 1250-1 180 1400-1 100 1260-1140 1150-1090

Comments Weak, narrow Weak, narrow Very strong Strong Strong Strong Strong Strong to medium

trithiocarbonates xanthates trithiocarbonates xanthates thiocarbonates thioureas xanthates xanthates

6.1 0 Sulfur-Containing Functional Groups

285

Examples (v in c m - ] )

in CCI,: 1718 1677 1640

Lo ‘s .f,

neat: 1076

s/

in ~ ~ 1 4 : 1083 1079 gas: # 2593 HSKO’2548 neat: 2470

in CC14: 1662

in CS,: 2562 2522

J , ;7;7C14:

in CC14:

in CC14: 1719

,k0’ ‘0

solid: 1212

,k0‘ 0

solid: 1234

solid: 1400

I

I

I

I

S

6 IR

286

6.1 1 Carbonyl Compounds 6.1 1.1 Aldehydes

%T C-H comb

c=ost 7-

3600

2c00

2doO

1600

1200

800

400

Typical Ranges ( v in c m - l ) Assignment C-H comb

c=o st

c=x

C-H 6

Range 2900-2800 2780-2680

Comments Weak, Fermi resonance with C-H 6 at =1390 For extreme position of C-H 6 only one band

Subranges: 2830-2810, Aliphatic 2720-2690 Aromatic, for o-substitution often higher 2830-28 10, 2750-2720 In the same range: cyclohexanes at ~2700,weak 1765-1645 Strong Subranges: 1740-1720 Aliphatic 1765-1730 &Halogenated aliphatics 1710-1685 Aromatic 1695-1660 a$-Unsaturated aromatic 1670-1645 With intramolecular H bonds 1390 Weak, of no practical significance


287

Examples (v in mi1) CH3CHO

1748

CC13CHO

1760

x1c7c14:

CHO

b"

1696

in CHC13: 1710 AN,

NO2

6.1 1.2 Ketones

Typical Ranges (v in c m - l ) Assignment

c=o st

Range 1775-1650 Subranges: ~1715

c=x Comments Strong Aliphatic, branching at a-position causes shift to lower frequencies:

\8-

~1775-1705

-1695

-1685

Cyclic, v decreases with increasing ring size [contd.]

2aa

6 IR

Assignment

Range

Comments

8 Conjugated:

-1675

-1775

e;

-1750

1650-1600

a$-Unsaturated, often 2 bands (rotational isomers) c=cst

-

a,p;y,&Unsaturated; a ,p;a',p'-unsaturated

=1695

1665

d

a

=

l

-1670

&

C

-1690 -1675

Aryl ketones

&a Diary1 ketones, with N or 0 in p-position: down to -1600 Shifted toward higher wavenumbers depending on dihedral angle cp between C=O and C-hal; largest effect for cp = Oo, no effect for cp = 90° Maximal shifts:a-chloro -25 a-bromo =20 a,a-dichloro 4 5 a-iodo 4 a,a'-dichloro 4 5 a,a-difluoro -60 perfluoro 40

-1665 &Halogenated ketones:

a-Diketones:

c; x 2

p-diketones:

-1720 -1775, -1760 ~1760 -1730 1675 =I680 1675 1720 -1650 -1615

--

Aliphatic Aliphatic 5-ring Aliphatic 6-ring Aliphatic enolized, C=C st: ~ 1 6 5 0 Aromatic o-Quinones, withperi-OH: -1675, =I630 Keto form, sometimes doublet Enol form Enol with intramolecular H bonds, C=C st: -1600 strong


Assignment y-diketones:

Range =1675

C=C=O st as

2155-2130

289

Comments As monoketones p-Quinones, with peri-OH: ~ 1 6 7 5~, 1 6 3 0 ; C=C st: ~ 1 6 0 0 Verystrong

Examples ( v in c m - l )

6

&

1691

&

/

s-trans

1672 1660

& l

d

1664

(rotamers) 1726

s-trans 1690 S-cis 1707

s-cis

(2222)

1639 ‘N

1648

N’

I

I

1752 C

A &

1697

1

Cl3C

ca3

1780 1751

c1

1722

c=x

1724 (keto form) 0 1608 (enol form) 1635 1590

6 IR

290

6

1669

&

1675

1669

& &

1623

1662

OH 0

1678

0

0-H 6 ip

O-H 6 OOP

(free) 0-H st

Carboxylate Anions

%T

I

3600

2800

2000

1600

1200

800

400

6.11 Carbonyl Compounds

291

Typical Ranges ( v in c m - l ) Assignment COO-H st

Range Comments 3550-2500 intensity variable Subrunges: 3550-3500 Free, sharp, only in highly diluted solutions 3300-2500 H-bonded, broad, often more than one band In the same range also OH st, NH st, CH st, SiH st, SH st, PH st 1800-1650 Strong 1800-1740 Free (also in dicarboxylic acids) 1740-1650 H-bonded (dimer, also in dicarboxylic acids) Subrangesfor H-bonded C=O: 1725-1700 al-COOH 1715-1 690 CS-COOH 1700-1680 ar-COOH 1740-1720 hal-C-COOH 1670-1650 Intramolecular H bond 1440-1210 Of no practical significance

c=o st

OC-OH st, C-OH 6 OC-OH 6 OOp960-880

( C O O ) -st as 1610-1550

( C O O ) -st sy 1450-1400

(coo)-6

Examples

1

OH

-775 -925 =680 =600 (V

Medium, generally broad (only in dimers), in the same range: =CH 6, ar CH 6 , NH 6 Very strong; in a-halogen carboxylates near the higher value, with more than one a-ha1 beyond the normal range; in polypeptides at -1575 Strong, of no practical significance, in polypeptides at ~ 1 4 7 0 Formates, weak Acetates Benzoates CF3COO'

in crn-l)

E;

in CCI,: 1756 1724

J O H

neat: 1759 1718 in CC1,: 1768 1717

OH

in CC14: 1704 solid: 1686

c=x

6 IR

292

neat:

neat:

in CC14:

+ ' OH

a q O H

neat: 1725

1730

1694

in CC14:

solid:

solid 0-

1605

';bOH NH3+

"3'

1740

)$OH

1788 1725

0

solid:

solid:

1735

$O ''H 0

solid: H o d o H 1724

0

doHgoH solid:

solid:

OH 1690

!{?&4:

0

in CHC13: 1706

0

solid:

OH

OH

in CC14:

1696

1696

in CHC13:

9

1661

6.1 1.4 Esters and Lactones

C-X

C=O st 3600

2800

2000

1600

C 0 - 0 st as 1200

I

800

400


293

Typical Ranges (v in c m - l ) Range 1790-1650 Subranges: 1750-1 735 Conjuguted esters: 1730-17 10 1730-1715 1690-1670 17961740 ~1760 ~1760 ~1735 Diesters: Keto esters: 1755-1725 =1750 (ketone) ~ 1 7 3 (ester) 5 1650

Assignment c=o st

-

Lactones:

Comments Strong Aliphatic esters a$-Unsaturated esters Aromatic esters With intramolecularH bonds a-Halogenated esters Vinyl esters, C=C st: 1690-1650, strong Phenol esters Phenol esters of an aromatic acid As the corresponding monoesters a-Keto esters, generally one band 0-Ketoesters,keto form P-Ketoesters, enol form, C=C st: ~ 1 6 3 0strong , y-Ketoesters, pseudoesters: -1770

~1840

-0 0

co Go -1770

~1800

0

9 0

~ 1 7 5 (additional 0 band at ~ 1 7 8 if 0 a-position free)

oo oo oo -1760

c-0

st

C - 0 st as:

1330-1050

~1720

2 bands: st as, very strong and at higher frequency; st sy, strong, at lower frequency

Subrunges: Formates, propionates, higher aliphatic esters ~1185 =1240 Acetates Z1210 Vinyl esters, phenol esters -1180 y-Lactones, &lactones Methyl esters of aliphatic acids -1165 In the same range: Strong bands for C-F st, C-N st, N-0 st, P-0 St, C=S St, S=O st, P=O st, Si-0 st, Si-H 6

c=x

6 IR

294

Examples (v in c m - l ) 1743

cq,f. 0-

1787

Br 1758 (1690)

1726

1730 (1658) (1638)

Ao/Si: I

0 % ’

40,

1725

1752 (1675)

1725

0

mo/

ester: 1704 ketone: 1690 \-O,)!.oq enol: 1645

0-

;7: 0

1760 1742

0

0

0

do/ 1737

O2N

0

1766

1743


295

6.1 1.5 Amides and Lactams Primary Amides

V

NH2 st 3600

c=ost 2800

2000

1600

I

1200

800

400

1200

800

400

1200

800

400

Secondary Amides

c=ost I

3600

2800

2000

3600

2800

2000

%

1600

c=oS t 1600

I

Typical Ranges (v in m i 1 ) Assignment N-H st

Range 3500-3 100

Comments Medium, in primary amides two bands, in proteins m d p l e t

Subranges: 3500-3400 Free 3350-3 100 H-bonded ~ 3 3 5 0=3 , 180 In primary amides generally two bands

c=x

296

6 IR

Assignment

Range Comments -3200, -3 100 In lactams generally two bands -3200 Monohydrazides -3 100 Dihydrazides -3250 Imides In the same range: OH st, fCH st (-3300, sharp), H20 C=O st (amide I) 1740-1630 Generally strong Subrunges: NH,C=O free amides, H-bonded: 1650 1690 -1685 NHC=O free amides, H-bonded: -1660 NC=O free amides, H-bonded: -1650 1650 ~1745 4-Ring lactams -1700 5-Ring lactams =1650 6-, 7-Ring lactams =1670 Monohydrazides -1600 Dihydrazides 1740-1670 Imides -1750, 1700 5-Ring imides, 2 bands 1655-1630 Polypeptides ~1690 Isocyanurates, with aromatic substitution at ~1770 1720 1755 sh Trifluoroacetamides NH 6 and 1630-15 10 Generally strong, absent in lactams st SY Subrunges: (amiden) -1610 NHzC=O free, H-bonded: -1630 -1530 NHC=O, H-bonded: -1540 1560-1510 Polypeptides -1555 Trifluoroacetamides C-N st (?) -1400 "2C=O -1250 "C=O -1330 Lactams NH 6 ip -1150 "2C=O 1465 Lactams NH 6 oop 750-600 NH2C=O -700 "C=O -800 Lactams

-

-

-

:":

x

-

-


297

Examples (v in crn-l) neat: 1672 in CHC13: 1709

H

solid:

AyOH

1631 in CHC13: 1679

1

H

H

I

JvvH

H

'

in CHC13: 1673

in cc14: 1690

JN-

1650

JNo

0

3

dm2 in 1678 CHC13:

H

N'

H solid: 1656

neat:

neat: 1672

L

in CC14: 1647

in cc14:

in CHC13: 1691 in CC14: 1705

1667

L

c x

solid

H

1505

1689

-z

in CCl4: 1753 1727

6 IR

298

solid: 1760 1690

p {

in CC14: 1721 1705

0

P(W P-OH st, broad, for P(OH)2 often two bands P-0-P st Strong R3P=0, also for R: H R2(RO)P=0, also for R: H R(R'0)2P=0, also for R: H (RO)3P=O R(H0)2P=O R(HO)P02-, more than one band ~ ~ 0 ~ 2 R2(HO)P=O R2PO2RO(H0)2P=O RO(HO)P02~ 0 ~ 0 ~ 2 (R0)2(HO)P=O (R0)2P02R(RO)(HO)P=O R(RO)P02-


Assignment

Range 1240-1205

Comments R 9 9 R R.‘P, ,P
2 Cn>2 chain chain (( dd zz 29, 29, 43, 43, 57, 57, ...). ...). Cleavage Cleavage of of the the C-0 C-0 bond bond with H rearrangement to give HCNO+' ( d z 43) or alkene+' ( d z 42, 56, with H rearrangement to give HCNO+' ( d z43) or alkene+' ( d z42, 56, 70,. 70,. ...). .). For 99. For cyanates cyanates with with Cn>5 Cn>5 substituents, substituents, alkene alkene elimination elimination to to yield yield m/z m/z 99. Ion 29, 43, 57,. .. Ion series: series: Saturated Saturated and and unsaturated unsaturated alkyl alkyl cations cations (C,H2n+l, (C,H2n+l, m/z m/z 29, 43, 57,. .. and CnH2n-1, m/z 27, 41, 5 5 , ...). Alkene radical cations (CnH2n, m/z 42, 56, and CnH2n-1, m/z 27, 41, 5 5 , ...). Alkene radical cations (CnH2n, m/z 42, 56, together with isobaric ions of the composition CnH2,NC0. 70,. .) together with isobaric ions of the composition CnH2,NC0. 70,. ...) Intensities: Intensities: Intensive Intensive peaks peaks mainly mainly in in the the lower lower mass mass range. range. Molecular ion: Usually weak or absent. [M-H]+ is often Molecular ion: Usually weak or absent. [M-H]+ is often more more intense. intense. Odd Odd mass mass for odd number of N atoms in the molecule. for odd number of N atoms in the molecule. 7 7 .. 9 9 .. 1 17 7 Aromatic Aromatic Cyanates Cyanates (R-OCN) (R-OCN) [8] [8]

Fragmentation: Fragmentation: Loss Loss of of OCN' OCN' (Am (Am 42) 42) or, or, to to aa lesser lesser extent, extent, of of CO, CO, with with subsequent HCN elimination (Am 28 and 27). subsequent HCN elimination (Am 28 and 27). Ion Ion series: series: Aromatic Aromatic hydrocarbon hydrocarbon fragments fragments corresponding corresponding to to CnHn CnHn and and CnHn, CnHn, 11 ( m / z 39, 51-53, 63-65, 75-77 ,...). ( m / z 39, 51-53, 63-65, 75-77 ,...). Intensities: Intensities: Intensive Intensive peaks peaks in in the the higher higher mass mass range. range. Molecular ion: Strong. Odd mass for odd number Molecular ion: Strong. Odd mass for odd number of of N N atoms atoms in in the the molecule. molecule. 7 7 .. 9 9 .. 1 18 8 Aliphatic Aliphatic lsocyanates lsocyanates (R-NCO) (R-NCO) [8] [8]

Fragmentation: Fragmentation: Spectra Spectra often often very very similar similar to to those those of of the the corresponding corresponding cyanates. cyanates. Cleavage of the C-C bond next to N, the charge remaining Cleavage of the C-C bond next to N, the charge remaining on on the the 'CH2NCO 'CH2NCO ( (d dz z 56) 56) for for short-chain short-chain isocyanates isocyanates and and preferably preferably on on the the alkyl alkyl substituent substituent for for compounds with a Cn,2 chain (m/z 29, 43, 57, ...). Cleavage of the C-N bond compounds with a Cn,2 chain (m/z 29, 43, 57, ...). Cleavage of the C-N bond with with H H rearrangement rearrangement to to give give HCNO+' HCNO+' ( ( dd zz43) 43) or or alkene+' alkene+' (( dd zz 42, 42, 56, 56, 70,. 70,. ...) .) ions. For isocyanates with Cn,5 alkyl chains, alkene elimination, yielding ions. For isocyanates with Cn,5 alkyl chains, alkene elimination, yielding d d zz 99. 99.

N N

346

7

Mass Spectrometry

+' m/z 99

Zon series: Saturated and unsaturated alkyl cations (CnH2n+l, d z 29, 43, 57,. .. and CnH2n-1, m/z 27, 41, 55, ...). Alkene radical cations (CnH2n, m/z 42, 56, 70,. . .) together with isobaric ions of the composition of CnH2,0CN. Intensities: Intensive peaks mainly in the lower mass range. Molecular ion: Usually weak or absent. [M-H]+ is often more intense. Odd mass for odd number of N atoms in the molecule. 7.9.1 9 Aromatic Isocyanates (R-NCO) [8]

N

Fragmentation: Consecutive elimination of CO (Am 28) and HCN (Am 27). In contrast to aromatic cyanates, practically no elimination of NCO' (Am 42). Zon series: Aromatic hydrocarbon fragments corresponding to CnHn and CnHnk1 (m/z 39, 51-53, 63-65, 75-77 ,...). Intensities: Intensive peaks in the higher mass range. Molecular ion: Dominating; base peak for phenyl isocyanate. Odd mass for odd number of N atoms in the molecule. 7.9.20 Aliphatic Thiocyanates (R-SCN)

[8]

Fragmentation: Elimination of HCN (Am 27) followed by loss of an alkyl group. The cleavage of the C-C bond next to SCN is unimportant except in short-chain thiocyanates. Zon series: Saturated and unsaturated alkyl cations (CnH2n+l,m/z 29, 43, 57,. .. and CnH2n-1, m/z 27, 41, 55 ,...>. Intensities: Intensive peaks in the lower mass range. Molecular ion: Weak. Decreasing with increasing chain length and degree of branching; absent from the spectrum of hexyl thiocyanate. Odd mass for odd number of N atoms in the molecule. Both [M+H]+ and [M-H]+ are detectable.


347

Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+'). 7.9.21 Aromatic Thiocyanates (R-SCN) [8]

Fragmentation: The most important fragmentation is the elimination of SCN' (Am 58). Further elimination reactions are loss of CN' (Am 26), HCN (Am 27), and CS (Am 44). Zon series: Aromatic hydrocarbon fragments corresponding to CnHn and CnHn+l (m/z 39, 51-53, 63-65, 75-77,...). Weak signal at m/z 45 (CHS+) indicates sulfur. Intensities: Intensive peaks in the higher mass range. Molecular ion: Dominant; base peak in phenyl thiocyanate. Odd mass for odd number of N atoms in the molecule. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+'). 7.9.22 Aliphatic lsothiocyanates (R-NCS) [8]

Fragmentation: Cleavage of the C-C bond next to NCS, leading to m/z 72 (CH2NCS) or to its homologues if the a- C atom is substituted. Loss of the alkyl residue with concomitant double hydrogen rearrangement to yield the protonated functional group (m/z 60). With a Cn>4 alkyl chain, loss of SH' (Am 33). With Cn>5 alkyl chain, loss of alkene leading to m/z 115, probably according to the mechanism shown for isocyanates. Zon series: Mainly saturated and unsaturated alkyl cations (CnHp+1, m/z 29, 43, 57,... and CnH2n-1, m/z 27, 41, 55,... ). Signal for CHzNCS (m/z 72) or its homologues (m/z 86, 100, 114,., .) if the a - C atom is substituted. Intensities: Intensive peaks mainly in the lower mass range. Molecular ion: Medium to weak, decreasing with increasing chain length and degree of branching. More intense than in the corresponding thiocyanates; 1% for hexadecyl isothiocyanate.Both [M+H]+ and [M-H]+are relevant. Odd mass for odd number of N atoms in the molecule. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+'). 7.9.23 Aromatic lsothiocyanates (R-NCS)

[8]

Fragmentation: Dominant loss of NCS' (Am 58). In contrast to aromatic thiocyanates, the loss of HCN (Am 27) or CS (Am 44) leads to very weak fragments only. Zon series: Aromatic hydrocarbon fragments corresponding to CnHn and CnH,* 1 (m/z 39, 51-53, 63-65, 75-77,...). Weak signal at m/z 45 (CHS+) indicates sulfur.

N

Next Page 348

7 Mass Spectrometry

Intensities: Intensive peaks in the higher mass range. Molecular ion: Dominant; base peak in phenyl isothiocyanate. Odd mass for odd number of N atoms in the molecule. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+'). 7.9.24 References

H. Schwarz, K. Levsen, The chemistry of ionized amino, nitroso and nitro compounds in the gas phase. In: The Chemistry of the Amino, Nitroso and Nitro Compounds and Their Derivatives; S . Patai, Ed.; Wiley: New York, 1982; p 85. D.G.I. Kingston, B.W. Hobrock, M.M. Bursey, J.T. Bursey, Intramolecular hydrogen transfer in mass spectra. 111. Rearrangements involving the loss of small neutral molecules, Chem. Rev. 1975,75, 693. R.D. Bowen, The chemistry of CnH2,,+2N+ ions. Mass Spectrom. Rev. 1991,IO, 225. K.-P. Zeller, Mass spectra of cyano, isocyano and diazo compounds. In: The Chemistry of Functional Groups, Suppl. C ; S . Patai, Z. Rappoport Eds.; Wiley: Chichester, 1983; p 57. C.W. Thomas, L.L. Levsen, Electron-impact spectra of 2-diazoacetophenones, Org. Mass. Spectrom. 1978,13,39. J.M. Miller, T.R.B. Jones, The mass spectra of azides and halides. In: The Chemistry of Functional Groups, Suppl. D; S . Patai, Z. Rappoport Eds.; Wiley: Chichester, 1983; p 75. R.A. Abramovitch, E.P. Kyba, E.F. Scriven, Mass spectrometry of aryl azides, J. Org. Chem. 1971,36,3796. K.A. Jensen, G. Schroll, Mass spectra of cyanates, isocyanates, and related compounds. In: The chemistry of Cyanates and Their Thio Derivatives; S . Patai, Ed.; Wiley: Chichester, 1977, p 274.

Previous Page 7.1 0 Sulfur-Containing Functional Groups

349

7.10 Sulfur-Containing Functional Groups [ i ] 7.10.1 Aliphatic Thiols [2]

Fragmentation: Elimination of H2S (Am 34; or SH, Am 33, from secondary thiols) followed by loss of alkenes; consecutive losses of ethylene from unbranched thiols. Cleavage of the a,P-C-C bond (next to the SH group) leads to CH2SH+ ( d z 47). Note that this fragment also occurs in secondary and tertiary thiols. The S atom is poorer than N, but better than 0, at stabilizing such a fragment. Cleavage at the next C-C bonds leads to signals at m/z 61, 75, and 89. In secondary and tertiary thiols, prominent fragments are formed by loss of the largest a-alkyl group. Zon series: Dominant consecutive alkenyl fragments (C,H2,-1, m/z 41, 5 5 , 69, ...) and smaller aliphatic fragments (CnH2n+l, m/z 43, 57, 71, ...). Sulfurcontaining aliphatic fragments: C,H2,+1S (m/z 47, 61, 75, 89, ...). Often significant sulfur-indicating fragments: HS+, H2S+', H3S+, and CHS+ ( d z 33, 34,35, and 45). Intensities: More intensive peaks in the lower mass range; mostly of the alkene type. Characteristic local maxima from S-containing fragments, CnH2,+1S (m/z 47, 61, 75, 89, ...). In n-alkyl thiols, the intensity of m/z 61 is roughly half that of m/z 47; the signal at m/z 89 is more intense than that at m/z 75, presumably because it is stabilized by cyclization. Molecular ion: Relatively strong except for higher tertiary thiols. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+'). 7.10.2 Aromatic Thiols [2]

Fragmentation: CS elimination from M+' and [M-l]+, yielding [M-44]+' and [M45]+. SH elimination from M+' to give [M-33]+. Zon series: HCS+ (m/z 45) is characteristic besides the aromatic fragments, C,H, and CnHnkl (m/z 39, 51-53,6345, 75-77 ,...). Intensities: Intensive peaks in the higher mass range. Molecular ion: Usually dominating; base peak in thiophenol. [M-l]+ is usually strong. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+').

S

350

7 Mass Spectrometry

7.1 0.3 Aliphatic Sulfides [ l ] Fragmentation: Loss of alkyl radicals by cleavage of the C-C bond next to S (the largest group being lost preferably) and of the C-S bond, followed by alkene and H2S elimination. Alkene elimination from M+' to form the corresponding thiol ions. In contrast to thiols and cyclic sulfides, no H2S or HS' elimination from M+'.

m/z 61

In general, the H rearrangements are non-specific. Secondary H transfer predominates over primary H transfer. Zon series: Sulfur-containing aliphatic fragments, CnH2n+lS (m/z 47, 61, 75, 89,. ..). The hydrocarbon fragments may dominate in long-chain sulfides. Intensities: Intensive peaks in the lower mass range. Characteristic local maxima from S-containing fragments, CnH2n+lS (m/z 47, 61, 75, 89, ...). Molecular ion: Usually strong. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+').

S

7.1 0.4 Alkyl Vinyl Sulfides

Fragmentation: Loss of alkyl radicals (Am 15, 29, 43, ...). Elimination of thioethanol (Am 62) after triple H rearrangement. Dominant m/z 60 (CH&H=S+') accompanied by m/z 61 (CH3CH2S+). Zon series: Sulfur-containing unsaturated aliphatic fragments, CnH2n-1S (m/z 45, 59, 73 ,...). Unsaturated hydrocarbon ions, CnH2, (m/z 42, 56, 70,...) and CnH2n-2 (m/z 40, 54, 68,...) Intensities: Intensive peaks evenly distributed over the whole mass range. Molecular ion: Of medium intensity. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+').


35 1

7.1 0 . 5 Cyclic Sulfides [3] Fragmentation: Primary cleavage of the C-C bond next to S, followed by rearrangements and elimination of CH3' (base peak for tetrahydrothiapyrane) and C2H.s'. In tetrahydrothiophene, [M-l]+ is also significant. HS', H2S, and C2H4 elimination from M+'. Zon series: Sulfur-containing aliphatic fragments with one degree of unsaturation, CnH2n-1S ( d z 45, 59, 73, 87, 101,...), d z 87 being of special dominance. Intensities: Overall distribution of peaks maximizing in the low mass range due to S-containing fragments, CnH2n-1S ( d z 45, 59, 73, 87,. ..). Molecular ion: Very strong. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+').

7.1 0 . 6 Aromatic Sulfides [2] Fragmentation: Loss of CS (Am 44) and of HS (Am 33) from M+'.

Zon series: HCS+ ( d z 45) is characteristic besides the aromatic fragments, CnHn and CnHnkl ( d z 39,51-53, 63-65,75-77 ,...). Intensities: Intensive peaks mainly in the higher mass range. Molecular ion: Strong. Characteristic 34S isotope peak at [M+2]+' and [Frag+2It for S-containing fragments (per S atom 4.4% relative to M+'). 7.10.7 Disulfides Fragmentation: Loss of RSS' leading to alkyl cations and alkene elimination to give RSSH+'. Cleavage of the S-S bond with or without H rearrangements, leading to RS+, [RS-H]+', and [RS-2H]+. Loss of one or two S with or without H

atoms is a common process in cyclic, unsaturated, and aromatic disulfides. Zon series: In saturated aliphatic disulfides, H2S2 and its alkyl homologues are characteristic ( d z 66, 80, 94,...). Intensities: Variable. Molecular ion: Usually strong. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+').

S

7 Mass Spectrometry

352

7.1 0.8 Aliphatic Sulfoxides [4,5] Fragmentation: Most fragments are produced after rearrangement with non-specific H transfer to the 0 atom and subsequent OH' elimination to yield [M-17]+ or alkene elimination to [M-alkene]+', followed by OH', SOH' (giving alk+ ions), or alk' elimination (yielding CH2=S-OH+, m/z 63).

1+.

R'-y&

-

- CH2=CHR2

OH I R2

1

-

1 +.

R'-S

YH

J+

-OH'

+

R

L

+

R-CH2 /SOH' m/z 29,43,57

CH&-OH m/z 63

Zon series: Characteristic ion at m/z 63 (CH2=S-OH+) as well as alkyl and alkenyl fragments, CnH2n+l (29, 43, 57, 71,...) and C,H2n-1(27, 41, 5 5 , 69,...). Intensities: Intensive peaks evenly distributed over the whole mass range. Molecular ion: Of medium intensity. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+for S-containing fragments (per S atom 4.4% relative to M+').

7.1 0 . 9 Alkyl Aryl and Diary1 Sulfoxides [4,5]

s

Fragmentation: Most fragments of methyl aryl sulfoxides are produced, after rearrangement to CH3S-O-ar+', by elimination of CH2S (yielding [M-46]+', a phenol), of CO (to [M-28]+'), and of CH3'. (to [M-15]+). The latter ion loses CO to give the thiapyranyl cation (m/z 97 if ar is phenyl).

of+'= eo-

- CH3'

S-+-

\

/CO [M-28]+'

m/z 112

I-CH2S

[M-15]+ m/z125

p o


353

The skeletal rearrangement is not relevant for the fragmentation of higher alkyl aryl sulfoxides. Here, direct cleavage of the C-S bonds and McLafferty rearrangements dominate. For diary1 sulfoxides, elimination of SO (to give [M-48]+’)as well as of 0, OH’, and COH’ (yielding [M-16]+‘, [M-17]+, and [M-29]+). After rearrangement to sulfenates, fragmentation of the S-0 bond to produce ar-S+ and ar-O+ ions, which further lose CS and CO, respectively, to give C5H5+ ( d z 65).

[M-16]+’

[M-48]+‘

Ion series: Besides the ions described under Fragmentation, mainly fragments of the aromatic type, Le., CnHn and CnH,*l ( d z 39, 51-53, 63-65, 75-77,...), as well as 0- and S-containing ions. Intensities: Intensive peaks mainly in the high mass range. Molecular ion: Very strong. Characteristic 34S isotope peak at [M+2]+’ and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+’). 7.1 0 . 1 0 Aliphatic Sulfones [4,51 Fragmentation: Fragmentation of the S-C bond with the charge remaining on either side. Single and double H rearrangements to give RS(O)OH+’ and RS(OH)2+. The probability of the double H rearrangement increases with increasing chain length. If one of the substituents is unsaturated, rearrangement to RS(0)O-alkene and fragmentation of the S-0 bond yields the ion RSO+’. Ion series: Dominating aliphatic fragments, CnH2,-,+1 ( d z 29, 43, 57,,..) and CnH2n-1 ( d z 27, 41, 5 5 , ...). Usually one significant fragment corresponding to alk-S(O)OH+’ (from the series of d z 80, 94, 108,...) or alk-S(OH)2+ (from the series of d z 81,95, 109,...) can be observed. Intensities: Intensive peaks mainly aliphatic fragments in the lower mass range.

S

7 Mass Spectrometry

354

Molecular ion: Weak. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+').

-k

OH // I49c4-q OH m/z 123 (70%)

+.

- C4H7'

- C2H5'

4

m/z 178

-

c4H9s0;/

1 \-C4H9'

+

m/z 149

C4H9+ m/z 57 (100%) 7.1 0 . 1 1 Cyclic Sulfones [4]

Fragmentation: Dominant eliminations of SO2 (Am 64, followed by loss of CH3'), HS02' (Am 65, followed by loss of C2H4), or CH2SO2 (Am 78). Weak fragment at [M-17]+ due to OH' elimination. Zon series: Mainly unsaturated hydrocarbon fragments, C,H2,-1 (m/z 27, 41, 55, ...). Intensities: Intensive peaks in the lower mass range. Molecular ion: Moderate. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+').

s

7.10.12 Alkyl Aryl Sulfones [4] Fragmentation: Isomerization of M+' to ar-OS(=O)alk and formation of the phenoxy ion or the phenol radical cation with H rearrangement. The migration of the aryl group depends on the type of substituents. It is facilitated by electron donators and hindered by acceptors. Mainly in substituted or unsaturated alkyl derivatives also isomerization to ar-S(=O)O-alk(ene) and formation of ar-S=O+ (m/z 125 if ar is phenyl). Single and double H rearrangements to give ar-S(O)OH+' and ar-S(OH)2+. The probability of the double H rearrangement increases with increasing chain length. In some derivatives, SO2 elimination from M+' dominates. Substituents X of the alkyl group may migrate to the aryl group to yield X-ar-S=O+ ions. Zon series: Aromatic fragments, C,H, and C,H,+l ( d z 39, 51-53, 63-65, 7577,. ..), as well as S - and O-containing aromatic fragments at higher masses.


355

Intensities: Intensive peaks mainly in the higher mass range. Molecular ion: Strong. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+'). 7.10.13 Diary1 Sulfones [4,5]

Fragmentation: Predominant aromatic fragments of the type ar-O+ and ar-SO+ ( d z 125 if ar is phenyl), formed after migration of one of the aryl groups. The ar-S02+ ion is unimportant; ar+ is intense. Small fragments due to SO,, S02H', and S 0 2 H 2 eliminations (Am 64, 65, and 66, respectively). With alkyl substituents in ortho position, [M-OH]+ and [M-H20]+' are formed, upon which SO elimination follows. Zon series: Aromatic fragments, CnH, and C,Hnkl ( d z 39, 51-53, 63-65, 7577,. . .) and the S- and 0-containing aromatic fragments at higher masses. Usually, ar-SO+ ( d z 125 if ar is phenyl) is very strong. Intensities: Intensive peaks mainly in the higher mass range. Molecular ion: Strong. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+'). 7 . 1 0.1 4 Aromatic Sulfonic Acids [6]

Fragmentation: The most prominent fragment, [M-HS03]+ (Am Sl), is formed in a two-step process. In the first step, OH' elimination leads to a weak fragment ion [M-OH]+ (Am 17). If an alkyl group is present in ortho position, [M-H2S03]+' (Am 82) is formed instead of [M-81]+. Other important fragments are [M-S02]+' (Am 64), [M-HS02]+ (Am 65), and [M-S03]+' (Am 80). Ion series: Aromatic fragments, CnHn and CnHnkl ( d z 39, 51-53, 63-65, 7577,. . .), and 0-containing aromatic fragments at higher masses. Intensities: Intensive peaks mainly in the higher mass range. Molecular ion: Very strong. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+'). 7.10.1 5 Alkylsulfonic Acid Esters [6]

Fragmentation: Loss of alkyl by fragmentation of the C-0 bond with concomitant double H rearrangement to form the protonated sulfonic acid ion ( d z 97 for methanesulfonates), which then loses water. Loss of the alkoxy1 residue (fragmentation of the S-0 bond). Formation of an alkene ion from the sulfonate alkyl by a McLafferty-type rearrangement. In aryl esters, the phenoxy ion and the phenol radical cations dominate the spectrum. Ion series: Besides RS03H2+ and RS02+ ( d z97 and 79 for methanesulfonates), for aliphatic esters mainly alkene fragments. In aryl esters, aromatic fragments,

S

7 Mass Spectrometry

356

C,H, and C,H,*1 ( d z 39, 51-53, 63-65, 75-77,...), as well as 0-containing aromatic fragments at higher masses. Intensities: Intensive peaks in the lower mass range. Molecular ion: Small or negligible in alkyl esters; strong in aryl esters. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+'). 7.10.16 Arylsulfonic Acid Esters [6] Fragmentation: Dominating fragments resulting from cleavage of the S-0 bond (leading to the ar-S02+ ion), which loses SO2 ( d z 155 and 91 for p-toluenesulfonates). In alkylsulfonates with longer chains, double H rearrangement to give the protonated acid ( m / z 173 for p-toluenesulfonates). Zon series: Aromatic fragments, CnHn and C,Hn*l ( d z 39, 51-53, 63-65, 7577, ...). Intensities: Intensive peaks mainly in higher mass range. Molecular ion: Medium or weak. Characteristic 34S isotope peak at [M+2]+' and [Frag+2]+ for S-containing fragments (per S atom 4.4% relative to M+').

7.10.17 Aromatic Sulfonamides [61 Fragmentation: In N-alkylamides, the C-C bond next to N is split preferably. In N-arylamides, besides [M-S02]+' and [M-HSOz]+, the ions ar-S02+ and ar'-NH+ are formed.

+

\02

1-

so2 +.

j

-

so2

-

- HCN

C,jHs+ (100%) Zon series: Ions typical of the tosyl group: d z 155, 91, and 65. Molecular ion: In arylamides, M+' is dominant.


357

7 . 1 0.1 8 Thiocarboxylic Acid S-Esters [7] In contrast to esters, elimination of the alkyl radical from the thiol site is the major fragmentation process. Ethylene sulfide is eliminated from thioesters with longer alkyl chains. Aromatic dithiocarboxylic acid esters usually fragment in two steps to the aryl cation.

[M-601"

d z 121

7.1 0 . 1 9 References

[l] C.C. van de Sande, The mass spectra of ethers and sulphides. In: The Chemistry of Ethers, Crown Ethers, Hydroxyl Groups and Their Sulfur Analogues, Suppl. E; S . Patai, Ed.; Wiley: Chichester, 1980; p 299. 123 C. Lifshitz, Z.V. Zaretskii, The mass spectra of thiols. In: The Chemistry of the Thiol Group, Part 1; S. Patai, Ed.; Wiley: London, 1974; p 325. [3] Q.N. Porter, Mass Spectrometry of Heterocyclic Compounds, 2nd ed.; Wiley: New York, 1985. [4] K. Pihlaja, Mass spectra of sulfoxides and sulfones. In: The Chemistry of Sulphones and Sulphoxides; S. Patai, Z. Rappoport, C.G. Stirling, Eds.; Wiley: Chichester, 1988; p 125. [5] R.A. Khmel'nitskii, Y.A. Efremov, Rearrangements in sulphoxides and sulphones induced by electron impact, Russ. Chem. Rev. 1977,46, 46. [6] S. Fornarini, Mass spectrometry of sulfonic acids and their derivatives. In: The Chemistry of Sulphonic Acid Esters and their Derivatives, S. Patai, Z . Rappoport, Eds.; Wiley: Chichester, 1991; p. 73. [7] K.B. Tomer, C. Djerassi, Mass spectrometry in structural and stereochemical problems. CCXXV. Sulfur migration in [M-C2H A]+' of S-ethyl thiobenzoate, Org. Mass. Spectrom. 1973, 7 , 77 1.

s

358

7 Mass Spectrometry

7.1 1 Carbonyl Compounds [I-41 7.1 1.1 Aliphatic Aldehydes [5]

Fragmentation: Cleavage of the bond next to CO. The fragmentation of the hydrocarbon chain is similar to that in corresponding alkanes. McLafferty rearrangement with localization of the charge on either side, giving rise to CnH2n+' ( d z 28, 42, 56, ...) and, often less important, to CnH2nO+' ions ( d z 44, 58, 72, ...). At least one product (often both) is significant. Elimination of water from the molecular ion to give [M-18]+', occasionally very pronounced. Zon series: Dominating consecutive fragments of the series of CnH2n+l and CnH2n-10 (in both cases: d z 29, 43, 57, ...). Weaker fragments of the senes CnH2n-I ( d z 41, 5 5 , 69, ...) and rearrangement products, CnH2,, ( d z 28, 42, 56, ...). Intensities: Intensive peaks concentrated in the lower mass range. Local even-mass maxima from McLafferty-type reactions ([M-44]+' when aldehyde not substituted in a-position). Molecular ion: Only strong for molecules of low molecular weight; very weak for Cn,g. [M-l]+ may be more relevant than M+'. 7.1 1.2 Unsaturated Aliphatic Aldehydes

Fragmentation: Cleavage of the bond next to CO, leading to [M-l]+ (more significant than in saturated aldehydes), [M-29]+, and m/z 29. No McLafferty rearrangement occurs if the y-hydrogen atom is attached to a double bond or if there is a double bond in a$-position. Zon series: Fragments of the series of CnH2n-1 and CnH2n-30 (in both cases d z 41, 55, 69,...). MoZecuZar ion: Stronger than in saturated aldehydes. Usually, m-1]+ is relevant.

C=X 7.1 1.3 Aromatic Aldehydes

Fragmentation: Characteristic H' loss to yield the corresponding benzoyl ion, [M1]+, followed by decarbonylation to a phenyl ion, [M-1-28]+, of lower intensity. To a small extent also decarbonylation of the molecular ion, leading to [M-28]+'. Weak signal at d z 29 (CHO+). Zon series: Aromatic hydrocarbon fragments corresponding to CnHn and CnHn+l ( d39,~5 1-53, 63-65, 75-77,. ..). Intensities: Intensive peaks predominantly in the molecular ion region. Molecular ion: Usually prominent. [M-1]+ is strong.


359

7.1 1 . 4 Aliphatic Ketones

Fragmentation: Cleavage of the bond next to CO is the most important primary fragmentation. The charge can remain on either side. The acyl ions then lose CO. McLafferty rearrangement giving rise to CnH2nO+' ions (m/z 58, 72, 86,. ..). Consecutive rearrangements occur if both alkyl chains contain a y-H atom. Ketoenol tautomerism of the first rearrangement product is not a prerequisite for the second rearrangement to occur. Oxygen is sometimes indicated by weak signals at [M-18]+' and m/z 31, 45, 59. Fragmentation of the hydrocarbon chain similar to that in the corresponding alkanes. Zon series: Dominating consecutive fragments of the series C , H Z ~ +and ~ CnH2n-10(in both cases: m/z 29, 43, 57, ...), with maxima due to cleavage at the CO group to give acyl ions and their decarbonylation products. Weaker fragments in the series CnH2n-l (m/z 41, 55, 69, ...). Even-mass maxima, CnH2n0 (m/z 58, 72, 86,. . .), due to alkene elimination (McLafferty rearrangement). Usually, m/z 43 (CH$O+) is strong if an unsubstituted a-CH2 group is present. Intensities: Intensive peaks mainly in the lower mass range. Molecular ion: Relatively abundant, weak in long-chain and branched aliphatic ketones. 7.1 1 . 5 Unsaturated Ketones

Fragmentation: Cleavage of the bond next to CO, more favorably on the saturated side, is the most important primary fragmentation. The acyl ion then loses CO. The McLafferty rearrangement occurs neither when the unsaturated substituents are in a,P position nor when the only available y-hydrogen atom is attached to a double-bonded carbon. Molecular ion: Relatively abundant. 7.1 1.6 Alicyclic Ketones

Fragmentation: Major primary fragmentation by bond cleavage next to carbonyl, followed by loss of alkyl residue.

(for R' = H)

c=x

360

7 Mass Spectrometry

Prominent McLafferty-type elimination of larger alkyl groups in position 2 or 6 as alkenes. This rearrangement is very favorable; even aromatically bonded H atoms can rearrange. For cyclohexanones, a consecutive retro-Diels-Alder reaction can occur:

m/z 98

m/z 70

Oxygen is sometimes indicated by a weak signal at [M-18]+'. Zon series: Consecutive alkene fragments of the type of CnH2n-1 0: CnH2n-30 (for both: m/z 41, 5 5 , 69, ...) with maxima due to alkyl loss after nng opening next to the carbonyl group and H transfer. Prominent even-mass maxima by elimination of substituents at position 2 or 6 as alkenes via sterically favored McLafferty rearrangements. Intensities: Overall more intensive peaks in the lower mass range or even distribution of major peaks over the whole mass range. Local maxima from major fragmentation pathway. Molecular ion: Abundant.

7.11.7 Aromatic Ketones

c =x

Fragmentation: Dominant a-cleavage to give the benzoyl ion, followed by decarbonylation to a phenyl ion of lower intensity. a-Cleavage in acetophenone also produces the acetyl cation ( d z 43). Even-mass maxima due to alkene elimination via McLafferty rearrangement. CO elimination from diary1 ketones through skeletal rearrangements. Zon series: Aromatic hydrocarbon fragments corresponding to CnH, and CnHn,l ( m / z 39, 51-53, 63-65, 75-77 ,...). Intensities: Intensive peaks predominantly in the molecular ion region. Molecular ion: Strong.

7.1 1.8 Aliphatic Carboxylic Acids Fragmentation: Fragmentation of the C-CO bond leading to m/z 45 and to [M-45]+. Loss of OH' leading to [M-17]+; may be followed by decarbonylation. Cleavage of the y bond (relative to CO) leading to +CH2CH2COOH (m/z 73) if there is no branching on the a- and p-C atoms. Loss of H' (not the carboxylic one) leading to [M-1]+. Water elimination to give [M-18]+' if the alkyl group


36 1

consists of at least 4 C atoms; may be followed by decarbonylation. McLafferty rearrangement to m/z 60 (acetic acid) if there is no a-substituent. Zon series: Saturated and unsaturated alkyl ions mainly in the lower mass range (CnHzn+1 and CnH2,-l, m/z 29, 43, 57 ,... and 27, 41, 55,...). With long-chain aliphatic acids, CnH2,-102 series (m/z 59, 73, 87,. ..), exhibiting maxima for n = 3, 7, 11, 15,... (m/z 73, 129, 185, 241,... ). Even-mass maxima, CnH2n02 (m/z 60,74, 88,. ..), due to McLafferty rearrangements. Intensities: Intensive peaks due to the above mentioned ions. MoZecular ion: Generally detectable. Easily protonated to [M+H]+. 7.1 1.9 Aromatic Carboxylic Acids

Fragmentation: Pronounced loss of OH', leading to [M-17]+ and followed by decarbonylation (Am 28) to a phenyl ion of lower intensity. Water elimination to [M- 18]+' if a H-bearing ortho-substituent is present. Some acids decarboxylate (Am 44). Loss of CO (Am 28) from M+'. 0 m/z 118forX=CH2 m/z 1 1 9 f o r X = N H m/z 120 for X = 0

Zon series: Aromatic hydrocarbon fragments, C,H, and C,H,,1 (m/z 39, 51-53, 63-65, 75-77,...). Intensifies: Intensive peaks predominantly in the molecular ion region. Molecular ion: Strong. 7.11.10 Carboxylic Acid Anhydrides

Fragmentation: In the case of linear anhydrides abundant acyl ions due to cleavage next to carbonyl group. For cyclic anhydrides maxima due to decarboxylation (Am C = 44), followed by decarbonylation. Molecular ion: Weak or absent (especially in linear aliphatic anhydrides), easily protonated to [M+H]+. Relatively strong for phthalic anhydrides. 7.1 1.1 1 Saturated Aliphatic Esters

Fragmentation: Dominant fragmentation of the bonds next to the carbonyl C, leading to alk-CO+ (m/z 43, 57, 71,. . .; decreasing intensity with increasing length of the alkyl chain) and followed by decarbonylation, as well as fragmentation to COOR+ (m/z 59, 73, 87,...) and to alk+ (m/z 15, 29, 43,...).

x

362

7 Mass Spectrometry

Alcohol elimination to C,H 2,-?0 (m/z 42, 56, 70, ...), followed by decarbonylation (Am 28) or ketene elimination (Am 42). Alkene elimination from the acid side via McLafferty rearrangements, leading to C,H2nO? ( d z 60, 74, 88, ...). The larger alkyl group participates in the rearrangement if several y-H atoms are available. In the following example, the alternative process leading to [M-C2H4]+' is negligible.

Non-specific H rearrangements at the alcohol side (from M+' or the McLafferty product) lead to C,H2,02 and to the corresponding alkene, CnH2n ( d z 28,42, 56,. . .). In methyl esters of long chain acids, the ions [(CH&+4,COOCH3]+ ( d z 87, 143, 199,...) correspond to maxima. For esters of higher alcohols (at least C3), double H rearrangement to the protonated acid, C,H2,+102 ( d z 61, 75, 89, ...). a-Substituted esters may lose the substituent and then CO (Am 28) via alkoxy1 rearrangement. In an analogous reaction, P-substituted esters may eliminate ketene (Am 42). Besides usual ester reactions, specific rearrangements can be observed in formates.

- CO, - R2

+ ( d z 31 for R' = H)

C =X

Zon series: CnH2,+l ( d z 29, 43, 57,. ..) for the alkyl groups at the ester oxygen (except for methyl esters). CnH2n-l ( d z 27, 41, 55, ...). C,H2n-102 ( d z 59, 73, 87 ,...), exhibiting maxima for n = 4, 8, 12,... ( d z 87, 143, 199,...) in case of the methyl esters of long-chain acids. Even-mass maxima for CnH2,02 ( d z 60, 74, 88, ...) due to alkene elimination via McLafferty rearrangements on both sides of the carboxyl group. CnH2, ( d z 28, 42, 56, ...) as H rearrangement product from the alcohol side. Intensities: Intensive peaks due to above mentioned ions from the lower mass range. Molecular ion: Often of low abundance. Easily protonated to [M+H]+.

7.11.12 Unsaturated Esters a,p-Unsaturated esters: Loss of alk-0' followed by C=O elimination is the dominant fragmentation path. Also, loss of the &substituent yields a 6-membered oxonium ring:

U

Tr O C H 3 LR

'


+ - R'

363

0 + O C H 3 m/z 113

Significant difference between Z and E isomers of long-chain a,P-unsaturated esters: Single H rearrangement occurs with Z esters and double H rearrangements (leading to protonated acids) have been found for E esters. p,y- Unsaturated esters: Only slight qualitative, but significant quantitative differences have been observed as compared to a$-unsaturated esters. y,6-Unsaturated esters: Loss of the alcohol chain as a radical, R', followed by ketene elimination. Aliphatic enol esters and aryl esters: Formation of alk-CO+ (m/z 43, 57, 71,...). Elimination of a ketene to give the enol/phenol radical cation. The rearrangement occurs prodominantly, but not exclusively, through a 4-membered transition state.

R40aJ +'

-RCH=C=Z

HO

G

l

+

*

[M-42]+' for R = H

7.11.13 Esters of Aromatic Acids Fragmentation: Dominant loss of RO' to form the benzoyl ion, followed by decarbonylation (Am 28) and further loss of acetylene (Am 26). Ethyl esters also eliminate C2Hq (Am 28) to give the acid radical cation, which then loses OH' to yield the benzoyl ion. In higher alkyl esters, besides the acid, the protonated acid is formed (double H rearrangement). In ortho-substituted aryl esters with an a-hydrogen atom on the substituent, an alcohol is eliminated from M+'. In the case of alkyl phthalates (other than dimethyl phthalate), alkenyl elimination to give the protonated ester acid, followed by alkene elimination from the other ester group, and subsequently water elimination to the protonated anhydride ion, which forms the base peak at m/z 149. Zon series: Aromatic hydrocarbon fragments, CnHn and C,Hnel (m/z 39, 51-53, 63-65, 75-77,. . .). Intensities: Prominent maximum at the mass of the related benzoyl ion and its decarbonylation product. Molecular ion: Usually strong.

c=x

364

7 Mass Spectrometry

7.11.14 Lactones Fragmentation: The most prominent reaction is the loss of substituents (or H') at the 0-bearing C atom, followed by decarbonylation (Am 28), decarboxylation (Am 44, mainly in smaller molecules), and ketene elimination (Am 42). Decarboxylation of M+' is rarely significant. Competing reactions are several kinds of primary ring cleavages. Aromatic lactones show maxima due to two consecutive decarbonylations. Zon series: No specific ion series. The acetyl ion ( d z 43) is often an important fragment. Intensities: Maxima at the mass resulting from loss of substituents at the C atom next to oxygen. Otherwise, intensive peaks evenly distributed over whole mass range. Molecular ion: Usually of low intensity and easily protonated to [M+H]+ in aliphatic lactones; abundant in the case of aromatic lactones.

7.11.15 AI iphatic Am ides Fragmentation: Alkene elimination on the acid side via McLafferty reaction to yield the corresponding acetamide radical cation. Loss of alkenes on the amine side to give the ion of the desalkyl amide, often via double H rearrangement to the protonated desalkyl amide ion. Cleavage on both sides of the carbonyl group. Cleavage of the C-C bond attached to N, and the p,y-C-C bond (relative to N; see scheme).

IIUZ 44

Cleavage of the bonds to the p-C (see scheme) and y-C on the acid side.

c=x

Zon series: Even-mass fragments corresponding to CnH2,N0 ( d z 44, 58, 72,. ..) produced by cleavage of the bond next to CO on the acidic side. Odd-mass fragments (in secondary and tertiary amides), CnH2n-10 ( d z 43, 57, 71, ...), produced by cleavage of the bond next to CO on the amme side. Intensities: Overall peak distribution maximizing in the low mass range. Local maxima from McLafferty and from y-cleavage products. Molecular ion: Significant. Strong tendency to protonate to [M+H]+.

7.11 Carbonyl Compounds

365

7.11.16 Amides of Aromatic Carboxylic Acids

Fragmentation: Amides of aromatic acids exhibit maxima due to amide bond cleavage yielding the benzoyl ion, followed by decarbonylation (Am 28). Zon series: Aromatic hydrocarbon fragments corresponding to CnHn and CnHn+1 ( m / ~39, 51-53, 63-65, 75-77 ,...). Intensities: Intensive peaks predominantly in the molecular ion region. Molecular ion: Abundant. [M-H]+ is significant in N,N-disubstituted anilides, weaker in monosubstituted derivatives, and absent from the spectrum of benzamide. It is formed exclusively by loss of ortho-hydrogens of the aromatic ring. 7.11.17 Anilides

Formanilides: Loss of CO (Am 28) to give the aniline radical cation and consecutive HCN elimination (Am 27). Acetanilides: Ketene elimination to yield the aniline radical cation (often base peak), which consecutively eliminates HCN (Am 27), and formation of the acetyl cation (m/z 43). Trichloroacefunilides: Dominant loss of CC1,' (Am 117). Pivalanilides: Besides reactions analogous to those of acetanilides (formation of the aniline radical cation, Am 84), also formation of the tert-butylbenzene radical cation through elimination of HNCO (Am 43). 7.11.18 Lactams

Fragmentation: Cleavage of the C-C bond at the N-bearing C atom. Cleavage of the CO-N bond, followed by loss of CO (Am 28) or by further cleavage of the C-C bond next to N, giving an iminium ion. In 2-pyrrolidone and 2-piperidone, the signal at m/z 30 ([CH2=NH2]+) is strong. The base peak of 2-pyridone is formed by CO elimination (Am 28).

c=x

7 Mass Spectrometry

366

2-Pyrrolidone:

- C2H5'

+ CH2=NH;! m/z 30

CH2=N=C=O

+

H m/z 56

2-Pipendone:

*$+ H2*c% J

0

0 1 ' + H

m/z 99

CCH*'+

N,c=o H m/z 99

d z 99

+ CH2=NH2 m/z 30

H m/z 99

N H

J

d z 71

d z 70 d z 55

c =x

Molecular ion: Often observable; more abundant than for the corresponding lactones.


367

7.11.19 Imides

Saturuted acyclic imides: Consecutive CO (Am 28) and alkoxy elimination:

J)NL.&,?

+. -c,o

A

1+- - CH30’

0 ’

N

+

m h 56

I

I Ketene elimination:

+*

- CH2CO

I

-C=N-

- CH3’

H0-c~;m/z 58

I

If the N-substituent chain is sufficiently long, cleavages of the C-C bond next to N with or without H rearrangement. Cyclic imides: The spectra of saturated cyclic imides are almost identical to those of the corresponding diketones. Loss of HNCO (Am 43) from succinimide, followed by CO elimination (Am 28). Aroyl migration and loss of CO2 from aromatic cyclic imides.

Dibenzoylamine: Loss of CO to N-phenylbenzamide:

368

7 Mass Spectrometry

7.1 1 . 2 0 References

[l] J.H. Bowie, Mass spectrometry of carbonyl compounds. In: The Chemistry of the Carbonyl Group, vol. 2; J. Zabicky, Ed.; Wiley-Interscience: London, 1970; p 277. [2] S.W. Tam, Mass spectra of acid derivatives. In: The Chemistry of Acid Derivatives, Part 1 ; S . Patai, Ed.; Wiley: Chichester, 1979. [3] D.G.I. Kingston, J.T. Bursey, M.M. Bursey, Intramolecular hydrogen transfer in mass spectra. II. The McLafferty rearrangement and related reactions, Chem. Rev. 1974, 7 4 , 215. [4] D.G.I. Kingston, B.W. Hobrock, M.M.Bursey, J.T. Bursey, Intramolecular hydrogen transfer in mass spectra. 111. Rearrangements involving the loss of small neutral molecules, Chem. Rev. 1975, 75, 693. [5] A.G. Harrison, High-resolution smass spectra of aliphatic aldehydes, Org. Mass. Spectrom. 1970,3, 549.

c=x


369

7.1 2 Miscellaneous Compounds 7.12.1 Trialkylsilyl Ethers [ 1,2]

Fragmentation: Loss of alkyl attached to Si (preferential loss of larger groups). Cleavage of the C-C bond adjacent to 0, followed by alkene elimination. Loss of alkoxyl, followed by alkene eliminations. Elimination of trialkylsilanol. The R2Si-OR' cation has the tendency to attack, in an electrophilic manner and even over long distances, free electron pairs and n-electron centers, causing the expulsion of neutral fragments from the interior of the molecule via a rearrangement: Br-(CH2)lo-O-Si

-- C(CH3)3'

- (CH2)100

Am 57

Am 156

/ Br-Si+ \

Zon series: [CnH2,.,+30Si]+ ( d z 75, 89, 103, 117,...). [CnH2,.,+3Si]: ( d z 45, 59, 73, 87, ...). Occasionally, maxima at even mass due to elimination of trialkylsilanol. Molecular ion: M+' often of low abundance or absent, easily protonated to [M+H]+. Typical isotope patterns owing to 28Si, 29Si, and 30Si (see Chapter 2.5.5).

7.12.2 Alkyl Phosphates [3]

Fragmentation: Maxima due to alkenyl loss from M+' via double H rearrangement, followed by successive alkene eliminations down to protonated phosphoric acid ( d z 99). Zon series: PO+ (m/z 47), H2P02+ ( d z 65), H2PO3+ ( d z S l ) , often as nonspecific P indicators. Molecular ion: M+' observable. 7.1 2.3 Aliphatic Phosphines and Phosphine Oxides

Zon series: Maxima of the ion series of [CnH2,.,+3P]+( d z 48, 62, 76, 90,. ..) due to alkene eliminations. Molecular ion: M+' observable.

Misc

370

7 Mass Spectrometry

7.1 2.4 Aromatic Phosphines and Phosphine Oxides Fragmentation: Maxima due to loss of an aryl group, followed by H2 elimination to yield the 9-phosphafluorenyl ion ( d z 183). Molecular ion: M+' abundant, easily losing H' to give [M-l]+.

m/z 183

7.12.5 References [ 11 D.G.I. Kingston, B.W. Hobrock, M.M. Bursey, J.T. Bursey, Intramolecular

hydrogen transfer in mass spectra. 111. Rearrangements involving the loss of small neutral molecules, Chem. Rev. 1975, 75, 693. [2] H. Schwarz, Positive and negative ion chemistry of silicon-containing molecules in the gas phase. In: The Chemistry of Organic Silicon Compounds;.S. Patai,, Z. Rappoport, Eds.; Wiley: Chichester, 1989; p 445. [3] D.G.I. Kingston, J.T. Bursey, M.M. Bursey, Intramolecular hydrogen transfer in mass spectra. 11. The McLafferty rearrangement and related reactions, Chem. Rev. 1974, 74, 215.

Misc.

7.13 Spectra

371

7.13 Mass Spectra of Common Solvents and Matrix Compounds 7.13.1

Electron Impact Ionization Mass Spectra of Common Solvents The label (50) indicates that the intensity scale ends at 50% relative intensity and is subdivided in 10% steps. In these cases, the height of the base peak has to be doubled to bring it to 100%.All spectra represent positive ions only. Water { 50}

Methanol

Acetonitri1e

Ethanol { 50)

Dimethyl ether

Acetone ( 5 0 )

Acetic acid

Ethylene glycol { 50)

,)[, ,,3:

6[ , , , ,

,1,5,

29 Tetrahydrofuran (50)

II

62 Pentane

, , ,

,I

Furan

;,

14

, 9J

,6[ , ,

,

29

N,N-Dimethylformamide

Solvents

7 Mass Spectrometry

372

Methyl acetate { 50)

4

Diethyl ether

Carbon disulfide { 50)

Pyridine

Benzene-dg { 50)

143

Benzene {SO)

I

78

Cyclohexane

1

52

I 79

1-Hexene

Methylene chloride

1

1,CDioxane ( 50}

Ethyl acetate { 50}

Hexane

I 57

1

Tetramethylsilane { 50)

Dimethyl glycol { 50)

Toluene

I

i

I 91

Diisopropyl ether { 50)

Butyl acetate { 50)

1

I

I

I 27

45

87 59 69

102

4 3 ~

js6

7.13 Spectra

373

j 1 ,7;l,i;,,I, Chloroform

Chloroform-d

118

I

Trichloroethylene

, 119 , ,

I

,(

,

Carbon tetrachloride

129

35 7759 ,

I

I

I

I

;" 4' 1

1

1

1

I

82 ,

I

94 I

,

l r ,;.{,

I

I

l

l

1

I

1

1

I

II 1

1

,ah l

I

203 223

i765 76 93 105 121 I

, , , , , , , , , , ,

I

I

1

168 182

l I

I

I

I

I

278 I

I

I

I

I

I

I

I

I

I

Dioctyl phthalate (frequent impurity due to its use as polymer plasticizer)

1

57 28 43 I

71

83g29:04113 132 I,.I1 ,.l,.j.&,l, ,. , I , , U ; ,*

~

167 .

,

1,

279

, , , , , , , , , , li ,

,

Heptacosafluorotributylamine(calibration reagent)

Solvents

7 Mass Spectrometry

374

7.1 3.2 Spectra of Common FAB MS Matrix and Calibration Compounds Fast atom bombardment (FAB) mass spectra (MS) usually exhibit protonated or deprotonated molecular ions, [M*H]*, and protonated clusters, [M,+X,kH]' (n,m = 0,1,2,...), of the sample and matrix molecules, X. If there are even traces of metal salts in the sample, clusters of the type [M,+X,+metal cation]+ occur in positive ionization mass spectra. Sodium (23 u) and potassium (39 u) ion adducts are most commonly encountered. The nature of the clusters is often revealed by the regular intervals at which they occur in the spectra.

Calibration Compounds in Positive Ionization FAB Mass Spectra Ultramark 1621 (erroneously also referred to as "perfluoroalkyl phosphazine")

:654

766

866 878

Polyethylene glycol 400 (often used as an internal reference for high resolution m/z determinations) 547

591

il

6?5

679

' ' ' ' I ' '

I . ,

500 1007

550 45

50

650

73 0

Solvents

600

50

! '

723 I '

700

I . 8

' I ' ' ' ' I '

750

283

177 . 100

150

200

250

"

' I ' ' ' ' I ' ' ' ' I ' ' ' '

800

300

850

327

371

350

900 415

400

950

I

1000

459 450

500

7.13 Spectra

375

Polyethylene glycol 600 (often used as an internal reference for high resolution m/z determinations)

50 1 0'

73 ' ' ;

100:

.y,'*

:'A.

I

0.8 177

113

89 "

"

I '

283

50

0

100

371

459

415

*

. ' I

57.0 93.1 132.9 185.1 45.0 75.0

50;

327

150

225.0 392.7 448.9 277.1 317.0 356.8 409.0 484.8

200

250

300

350

400

500

450

Matrix Compounds in Positive Ionization FAB Mass Spectra

136 154 5:

289 307 1

50 1 0'

~

~

"

', :'

"11.

'1.

"

~

'

I '

"

' I

"

8 ' .

I

"

'

I

-

~

~

~

460 '

" 1" I ~

"

k,, ~

, 1

277

101

45 57 75 3

1

L' I 1

'

I . ,

' I

369

"

"

I '

!

' ' I

46 1

"

"

I ; '

"1

~

~

~

'

7 Mass Spectrometry

376

541

3.0;

1'5j 525 0.0-

8

rl-

569 I

3

/!

*-',

613 I

657

,',

.,

1 1 ,

7

1'

r

I-1

'

' 1

'

r

'

i

'

--

7

1

7

7

8

' '

i

I

7

309 l 0 i 259 , , ,391 ; I , , , , I46 , 1 ' " ,

, I , , , , :4,J.:;al

789 ~

500

~

550

~

~

600

~

~

650

'p3

~

~

~

"

I

~

"

700 750 800 219 265 177 221

~

I

"

850

~

I

~

950

'

I

'

1000

i

i " ! ' l ' " ' ~ ' i ' ~ " l~ ' ~ " ' I " i " ' *

0 50 100 150 200 2-Nitrophenyl octyl ether (M, 25 1)

600

"

900

650 140

700

I

"

9

'

I

250

300

350

400

450

500

2r

800

850

900

950

lo00

250

300

750

221 235

lo{

333 364 Y

l

47 1486

'.

I " ' " " ' " ' ' " 1 ' ' " I ' ' ~ ' 1 ' " ' I ~ '

Solvents

0

50

100

150

200

350

400

450

500

~

~

~

I

Spectra

7.13

0.5:

377

597

0 . 0 " " ' " " . ~ " " ' " ' ' ' ~ " " ~ ' ' " ~ " ' ~ " ' ' I ' ' ' ' ~ " ' ' r

118

50 {

o

150

304%6 74

:

5'

194

132

: I . ' . i'

+I".

8

'

4: 267 : 281

J '

'

'

I

'

448

?

.'.;.,

~

~

,'',

' '

307 '

'

7

8

'

I *

8

7

..'-

-

8

8

I

1

60 1

~

-

~

.

~

~

105 87

~

,

.

~

'

~

.

:

,

~

~

~

~

24 1

12'

1

;

151 ;66

2251

286

48 1

690

5'

o-....

7

"

'

608 +'"

...?

"

"

80 120 148 176 204 1

'

50 1 501 545

589

1

L

1

L

L

,

,

"

'

"

'

"

1

"

"

"

"

' . "

304

,I

633 679

721

Solvents

,

7 Mass Spectrometry

378

Polyethylene glycol 600 (often used as internal reference for high resolution MS)

0

50

100

150

200

250

300

350

400

450

Ultramark 1621 (erroneously also referred to as "peffluoroalkyl phosphazine")

50

Solvents

59.0 91.0

19.0

392.8 422.8

1

500

7.13 Spectra

379

Matrix Compounds in Negative Ionization FAB Mass Spectra 3-Nitrobenzyl alcohol (M, 153) 1007

306 50i

459

352

0'

1 -

I " " I

A,,

,

25 ! 55 1 O

'

.

-

~

,

643 i

~

91

~

-

~

735 I

~

~

-

-

I

.

.

-

183

59 71

64 89

367

139 179

197

287

377

459

467

Solvents

7 Mass Spectrometry

380

2-Nitrophenyl octyl ether (M, 25 1)

~

500

~

~

550

~

600

"

~

"

650

"

~

700

.

'

"

'

~

'

'

750 800 25 1

~

'

850

'

'

'

900

~

'

~

950

~

~

1

'

~

'

'

lo00

470 "

50

0

100

150

200

250

300

'

I

350

~

*

"

400

I

~

'

450

'

~

I

~

~

~

*

500

2-Nitrobenzyl alcohol solution of hexadecylpyridiniumbromide (M, 385; hexadecylpyridinium = 304; enhances detectability and reduces metal ion adducts of sample [3].) 100 50 0 500

0

845

L

.

550 600 79

650

700

750

800

850

900

950 462

1000

50

150

200

250

300

350

400

450

500

100

7.1 3.3 Spectra of Common MALDI MS Matrix Compounds

Matrix-assisted laser desorption ionization (MALDI) mass spectra (MS) usually exhibit protonated or deprotonated molecular ions, [MkH]', and protonated clusters, [M,+X,kH]* (n,m = 0, 1, 2, ...), of the sample and matrix molecules, X. If there are even traces of metal salts in the sample, clusters of the type [M,+X,+metal cation]+ occur in positive ionization mass spectra. Sodium (23 u) and potassium (39 u) ion adducts are most commonly encountered. The nature of the clusters is often revealed by the regular intervals at which they occur in the spectra [4].

Matrix Compounds in Positive Ionization MALDI Mass Spectra 3-Aminoquinoline (M, 144)

I So'vents

289

A

L

6. ;o* 'lob' ''

WNH2

145

'26b' '2;o

433

'3k' 3 S O '4b'4;b:'Sob' z '6& '6;o '7k ,;io '8bo

l

7.13 Spectra

381

a-Cyano-4-hydroxycinnamic acid (M, 189; m/z 212, [M+Na]+) I102 I

I

H

190

I,;,, .;,I.!,;,

myH

212

&

1"'~l"''l

0

I'

379

I ' " ' I ' " " ' " " ' " I " ' " ~ ' " I ' " ' ~ ' ~ " I ~ ~ ~ ~ I ' ~ " I ' ' ~ ' I

I

50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800

2,5-Dihydroxybenzoic acid (M, 154; m/z 177, [M+Na]+; m/z 193, [M+K]+)

I ' ~ ~ ' I ' ~ " I ' ' ' ' I ' ' ~ ' I

0

50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800

2,6-Dihydroxyacetophenone(M, 152; m/z 175, [M+Na]+; m/z 191, [M+K]+; m/z 365, [2M+Na+K-H]+ ?)

e.

153

H

23 39 175 191 i

b

L

,

I 0

, , ,

,,,,

,,,,

211 195 177

1

365 L L

L

- A

227

,,:;A

,,,, ),,,

H

,,,,

.

, , , , ,,.,

H

H

,,,, ,,,, ,,,,

,,,, ,,,, , , , ~

50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800

Ferulic acid (4-hydroxy-3-methoxycinnamicacid; M, 194)

H

37 I 389

7 Mass Spectrometry

382

Sinapinic acid (3,5-dimethoxy-4-hydroxycinnamicacid; M, 224; m/z 471, [2M+Na]+ )

'oTco

HO

/o

640 L I""I""I""I""I""I""I""I""I""I""I'~~"I""I""I""l''"l

0

50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800

Matrix Compounds in Negative Ionization MALDI Mass Spectra 3-Aminoquinoline (M, 144)

mNHz

285 I 295

N

437 1

. A .

I " " I " " I " ~ ' I " " I " " I " ~ ' I " " I ~ ~ ~ ~ ~ " ~ ~ ~ ~ ' " I ~ ~ " ~ ~ ~ " ~ ~

0

50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800

a-Cyano-4-hydroxycinnamic acid (M, 189; m/z 399, [2M+Na-2H]-)

99 110 ""I""1""I"'~l""I""1""1""I~"'I""I""~""I~"'~

t""I""I'"'

2,6-Dihydroxyacetophenone(M, 152; m/z 325, [2M+Na-2H]-)

I

HO 151

0

AA

Spectra

7.13

383

Dithranol (M, 226) 225 240

193

0

465

387

L.

688

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800

50

Ferulic acid (4-hydroxy-3-methoxycinnamicacid; M, 194)

I

0

'

~

50

~

~

I

~

~

~

'

I

'

~

~

'

I

~

'

~

'

I

'

~

~

~

I

~

~

~

'

I

"

'

~

I

~

~

"

I

~

~

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800

Sinapinic acid (3,5-dimethoxy-4-hydroxycinnamic acid; M, 224)

188

1223

447 HO ' T

O

o

H

/o

l""l~"'l""l""l""l""l~"'l""l""l'"'l''''l""l""l""l"'l

0

50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800

7.1 3.4 References R. Orlando, Analysis of peptides contaminated with alkali-metal salts by fast atom bombardment mass spectrometry using crown ethers, Anal. Chem. 1992, 64, 332. P.K. Singh, L. Field, B. Sweetman, Organic disulfides and related substances, J. Org. Chem. 1988, 53, 2608. Z.-H. Huang, B.-J. Shyong, D.A. Gage, K. R. Noon, J. Allison, N-Alkylnicotinium halides: a class of cationic matrix additives for enhancing the sensitivity in negative ion fast-atom bombardment mass spectrometry of polyanionic analytes, J. Am. SOC.Mass Spectrom. 1994, 5, 928. A.E. Ashcroft, Ionization in Organic Mass Spectrometry, RSC Analytical Spectroscopy Monographs, The Royal Society of Chemistry: Cambridge, 1997.

Solvents

~

8.1 Absorbed Radiation and Color

385

8 UVNis Spectroscopy

8.1 Correlation between Wavelength of Absorbed Radiation and Observed Color Absorbed light Wavelength [nm] 400 425 450 490 5 10 530 550 590 640 730

Observed (transmitted) color

Corresponding color violet indigo blue blue blue-green green yellow-green yellow orange red

purple

yellow-green yellow orange red purple violet indigo blue blue blue-green peen

8.2

UVNis Absorption of Simple Chromophores Chromophore Compound C-H CHA c-c CHi-CH3 c=c CH,=CH2 (CH3)2C=C(CH3)2 c=c=c CH2=C=CH2

c-c1 C-Br c-I

CH3C1 n-C3H7Br CH31

Transition

o+o* o+o* n+n* Z+X*

n+o* n+o* n+o*

h,, 122 135 162 196 170 227 173 178 196 222 173 208 259

E,,,

strong strong 15000 11500 4000 630 6000 10000 2000 160 200 300 400

Solvent gas gas heptane heptane

gas hexane hexane hexane hexane

386

8 UVNls

Chromophore Compound

Transition

c-0 C-N C=N

N=N N=O

C-N X=Y=Z J

c-s

n+o*

n+o* n+o* n+o* n+o* n+o*

c=s

h,

,E ,,

177 184 193 199

200 2500 2500 4000

265

15

193 265 340 300 665 276 218 313-384 260 490 250 230 270 195 235 194 225 194 250 460

2000 200 16

495

c=o

n+o* n+n* CH3COOH CH3COONa CH3COOC2H5 CH3CONH2

c=c=o

Q.

(C2H&C=C=O

n+n* n+n*

n+n* n+n* n+n*

Solvent hexane gas hexane hexane water

ethanol ethanol ethanol 100 ether 20 27

ethanol 1050 ethanol 20-40 ethanol 15 ethanol 1200 hexane 4000 25 1800 gas 180 4500 gas 1800 5500 hexane 380

Weak weak

ethanol

166 189 279 200 210 210 220

16000 gas

191

15200 CH3CN

227

900 15 50 150 50 63

360

hexane hexane gas water gas water

8.3 Conjugated Alkenes

387

8.3 UVNis Absorption of Conjugated Alkenes 8.3.1 UV Absorption of Dienes and Polyenes The n-n* transition of conjugated double bonds is above =200 nm with typical intensities of the order of log E = 4. Its position can be estimated with the Woodward-Fieser rule. For cross-conjugated systems, the value for the chromophore absorbing at the longest wavelength must be calculated.

Woodward-Fieser rule f o r estimating the position of the x-x* transition (Amax in nm) Parent system m

-

5

,' I

I. ,A. V

Increments

"

acyclic

217

heteroannular

214

homoannular

253

for each additional conjugated double bond

for each exocyclic double bond for each substituent

Solvent correction

c-

+30

+5

C-substituent

+5

c1

+5

Br

+5

0-alkyl

+6

OCOCH,

0

WlkYU2

+60

S - alkyl

+30

=o

388

8 UVNls

Example: Estimation of the absorption maximum for

n

base value (homoannular) 1 additional conjugated double bond 1 exocyclic double bond 3 C-substituents 1 OCOCHq estimated eXP

253 30 5 15 0 303

306

8.3.2

UV Absorption of a,P-Unsaturated Carbonyl Compounds The z-z* transition of a$-unsaturated carbonyl compounds is above =200 nm with typical intensities of the order of log E = 4. Its position can be estimated with the extended Woodward rule. For cross-conjugated systems, the value for the chromophore absorbing at the longest wavelength should be calculated.

Extended Woodward rule for estimating the position of the n-n* transition (Amax in nm)

S Parent system

@ fXo

P

X X: alkyl X: H X: OH X: 0-alkyl

215 207 193 193 215 202

8.3 Conjugated Alkenes

Increments

for each additional conjugated double bond

for each exocyclic double bond

Solvent corrections

+30

cK

+5

n 0

+39

for each homoannular diene system For each substituent on double bond system C-substituent c1 Br OH 0-alkyl 0-COCH3 S-alkyl NWYl)2

389

Increment

a

P

Y

6 and beyond

+IO +15 +25 +35 +35 +6

+12 +12 +30 +30 +30 +6 +85 +95

+18

+18

+17 +6

+50 +3 1 +6

Solvent water hexane cyclohexane chloroform methanol ethanol diethyl ether dioxane

Correction term -8 +11 +11 +1 0 0 +7 +5

Example: Estimation of the absorption maximum in ethanol for

base value 2 additional conjugated double bonds exocyclic double bond homoannular diene system 1 P-C-substituent 3 additional C-substituents solvent correction estimated exP

215 60

5 39 12 54 0 385 388

390

8 UVNis

8.4 UVNis Absorption of Aromatic Compounds 8.4.1 UV Absorption of Monosubstituted Benzenes

Typical Ranges f o r Monosubstituted Benzenes Transition n+n* (allowed) n+n* (forbidden) n+m* (substituent delocalized by aryl; K Band) n+n* (substituent with lone pair, R band)

hmax 180-230 250-290 220-250 275-350

E

2000-1oooO 100-2000 10000-30000 10-100

Specific Examples of Monosubstituted Benzenes

Substituent R (solvent) -H (cyclohexane) -CH3 (hexane) -CH=CH2 (ethanol) -C&H (hexane) -C1 (ethanol) -OH (water) -0- (water) -NH2 (water) -NH3+ (water) -NO2 (hexane) -CN (water) -CHO (hexane) -COCH3 (ethanol) -COOH (water)

n+n*

n+n*

n+n*

(allowed)

(forbidden)

(K band)

I,,,

h,,

h,,

E

198 8000 208 7900

210 211 235 230 203 208 213

7500 6200 9400 8600 7500 9800 8100

202 8000

E

255 230 262 230 282 450 278 650 257 170 270 1450 287 2600 280 1430 254 160 270 800

251

271 1000 280 1400 278 1100 270 800

224 242 243 230

n+n* (R band) E

h,,

E

244 12000 236 12500

9000 322

150

13000 14000 ~ 3 3 0 4 0 13000 319 50 10000

8.4 Aromatic Compounds

8.4.2 UV Absorption of Substituted Benzenes Estimation of the position of the allowed n-n* transition in multiply substituted benzenes (Amax in nm, log E: 4 ) Base value: 203.5 Substituent -CH3

-c1

-Br -OH -0-OCH3 -NH2 -NHCOCH3 -NO2 -CN -CHO -COCH3 -COOH

Increment rnml 3.0 6.0 6.5 7.0 31.5 13.5 26.5 38.5 65.0 20.5 46.0 42.0 25.5

391

8 UVNis

392

8.4.3 UV Absorption of Aromatic Carbonyl Compounds

Scott rules for estimating the position of the K band (solvent: ethanol; Amm in nm, E 10000-30000) Parent system:

dH

doH doR

250

230

R

VIk /

Increments

246

230

Substituent

Ortho

meta

pmn

-alkyl

3

3

10

-cycloalkyl

3

3

10

-c1

0

0

10

-Br

2

2

15

-OH

7

7

25

-0-alkyl

7

7

25

-0-

11

20

78

-NH2

13

13

58

-N(CH3)2

20

20

85

-NHCOCH3

20

20

45

Example: Estimation of the absorption maximum (K band) for

‘0

base value ortho -cycloalkyl para -0-alkyl estimated exP

246 3 25 274 276

8.5 Reference Spectra

__

393

8.5 UV/Vis Reference Spectra 8.5.1 UV/Vis Spectra of Alkenes and Alkynes

5-1

I

0l 200

log&

log E

41r

200

1 400

hlnm

log E 54-

H

3-

0 200

? ,,

I

300

400

’

h/nm

400

,

,

, ,

h/nm

“i\L -To

1

1300

OH

\

2

2-

200

h / nL m

- - - -

HO

:I,, 34

300

400

- - - 4

3

0

300

200

300

400

hlnm

8 UV/Vis

394 log E

5-

-Yo OH

4-

5-

-Yo 0-

321-

200

hlnm

400

300

200

hlnm

400

300

8.5.2 UVNis Spectra of Aromatic Compounds log E 5-

log E 5-

4-

4-

3-

3-

2-

2-

1-

1-

0

1

1

1

,

~

1

1

1

1

~

,

1

log E

5-

6

I?.:

:; 21

1

hlnm

400

300

200

2l hlnm

400

300

200

5-

4-

32-

1-

0 200

I

I

I

I

I

300

I

I

I

I

,

400

I

I

I

I

hlnm

0

I

,

I

I

I

,

I

I

I

1

8

I

I

I

1

1


log E 5-

6

4-

32-

IogL 4

2

1

1-

0

395

1

1

1

1

,

,

1

1

1

,

9

8

8

1

200

300

log E 5Iog51

lol-h

400

hlnrn

I

2

1

200

h/nrn

400

300

200

300

400

hlnrn

!/y 21

0 l 200

L hlnrn

400

300

200

300

400

hlnrn

200

300

400

h/nm

log E 5

6

:!\ 2

1-

0

~

l

l

l

,

l

l

r

l

)

I

I

I

I

396

0 200

8 UV/Vis

1 300

400

hlnrn

200

300

400

hlnrn

200

300

400

hlnrn

Q"-o / /

log5E

4 1 v 3

0 l 200

400

hlnrni

300

log E

4:L e 5

23 -

-

0 200

1

300

400

htnm

300

400

k f nL rn

2

0 I 200

Iogh 2

1-

200

300

400

hlnrn


5-

5-

4-

4-

d

log E 5

::\

log E

2-

1-

1I

,

I

I

~

I

I

,

I

~

I

,

,

log E

0

,

I

I

I

~

I

I

I

,

~

,

,

,

,

5

::-L:

::\

o a , H

2

2-

1

1-

I

log E 5-

I

I

J

~

I

,

,

I

~

,

,

,

0

,

,

J

,

,

d o -

,

,

,

,

,

~

7 ;: \

21 I

I

I

I

~

I

I

I

,

~

,

,

,

,

,

,

log E 5-

&

4

0

J

log E

5-

0

OUO

53:\ 4-

2-

0

397

,

,

0

,

I

,

,

~

P ,

,

,

,

~

,

,

,

,

8 UVNls

398 109 E 54-

321-

0 200

I

I

I

I

,

I

I

I

,

~

400

300

I

I

I

hlnm

I

hlnm

400

300

200 log E

54-

32-

\

11

0 200

1-

1 300

400

0

,

I

I

I

~

I

I

I

I

~

I

I

I

I

hlnm

log54E-

3-

2l

2-

1

0 200

1-

1 300

400

hlnm

400

hlnm

7 8

0

\

I

I

J

I

~

I

I

I

/

I

~

I

I

:p 2

&

1

0 200

/

/

300

200

300

400

hlnm

I

I


200

300

400

h/nm

5hlL 4

200

, ,

200

300

400

hlnm

200

300

400

hlnm

0 200

,

hlnm

400

300

'i,,

399

, ,

"",

,

300

400

hlnm

300

400

1 hlnm

0 200

8.5.3

UVNis Spectra of Heteroaromatic Compounds

'"%

Q

"19

H

2

1-

0 200

300

400

hlnm

I

I

I

I

,

I

I

I

I

(

~

~

~

~

8 UVIVis

400

log E

5-1

Iogh Q

2

1

200

300

hlnm

400

200

300

5-

0

432-

0 200

SG,

2

11

1

1

,

1

,

300

1

1

,

1

,

400

,

,

,

hlnm

hlnm

400

1L

0200

hlnm

400

300

log E

5$ N-N

'ld

1 200

300

400

hlnm

or" '

0 200

5

0

300

, 400

, , , ,

hlnrn

rn "..! H

2

2

, ,

I 1 o g h '

0 200

300

400

hlnm

200

300

400

hlnm


'i..-;

40 1

2

1

200

300

14

400

hlnm

2l 1

200

200

300

400

hlnm

300

400

h/nm

21 $

300

400

h/nm

200

8.5.4 UVIVis Spectra of Miscellaneous Compounds

:I

log &

CHC13

CHBr3

'r\

3

1

200

lik

300

400

hlnm

200

300

400

hlnm

log E

yBr

21

200

300

400

h/nm

YI

IOg5] 4

200

300

400

hlnm

402

200

8 UV/Vis

300

400

hlnm

300

200 log e 5-

CH3-NOz

hlnm

400

KSCN

4321-

0

200

300

400

hlnm

1

1

1

1

,

1

1

1

1

,

1

1

1

,

".

log E

21

3 2 ol- 1

0 200

300

400

h/nm

0 200

300

400

hlnm

300

400

hlnm

200

300

400

hlnm

1

1

IOg5] 4

200


200

.k

hlnm

400

300

403

.i-\

300

400

hlnm

200

300

400

hlnm

200

log E

4

2

0H

21

1

o

h 300

200

h/nm

400

8.5.5 UVNis Spectra of Nucleotides

./ybo 2

1-

0

1 I

I

I

I

,

I

I

I

I

,

I

,

,

,

200

1-

0

H

300

400

hlnm

300

400

hlnm

1-I 1

1

1

,

,

1

,

,

,

,

,

,

,

,

200

404

8 UVlVis

8.6 UVNis Absorption of Common Solvents The end absorption, Lend, of several common solvents is given here as the wavelength at which the solvents absorb 80% of the irradiated light (Lend in nm; cell length, 1 cm; reference, water). Solvent acetone acetonitrile benzene carbon disulfide carbon tetrachloride chloroform cyclohexane dichloromethane diethyl ether 1,4-dioxane ethanol

%nd 335 190 285 380 265 245 210 230 210 215 205

Solvent ethyl acetate heptane hexane methanol pentane 2-propanol pyridine tetrahydrofuran toluene 2,2,4-trimethylpentane xylene

Lend 205 195 195 205 200 205 305 230 285 210

290

Structure Determination of Organic Compounds: Tables of Spectral Data, Third Edition

Structure determination of organic compounds: tables of spectral data

Structure Determination of Organic Compounds: Tables of Spectral Data