1 Introduction ................................................. 1
1.1 Scope and Organization .................................. 1
1.2 Abbreviations and Symbols ............................... 3
2 Summary Tables ............................................... 5
2.1 General Tables .......................................... 5
2.1.1 Calculation of the Number of Double Bond
Equivalents from the Molecular Formula ........... 5
2.1.2 Properties of Selected Nuclei .................... 6
2.2 13C NMR Spectroscopy .................................... 7
2.3 lH NMR Spectroscopy .................................... 10
2.4 IR Spectroscopy ........................................ 13
2.5 Mass Spectrometry ...................................... 18
2.5.1 Average Masses of Naturally Occurring Elements
with Masses and Representative Relative
Abundances of Isotopes .......................... 18
2.5.2 Ranges of Natural Isotope Abundances of
Selected Elements ............................... 25
2.5.3 Isotope Patterns of Naturally Occurring
Elements ........................................ 26
2.5.4 Calculation of Isotope Distributions ............ 27
2.5.5 Isotopic Abundances of Various Combinations
of Chlorine, Bromine, Sulfur, and Silicon ....... 29
2.5.6 Isotope Patterns of Combinations of CI and Br ... 31
2.5.7 Indicators of the Presence of Heteroatoms ....... 32
2.5.8 Rules for Determining the Relative Molecular
Weight (Mr) ..................................... 34
2.5.9 Homologous Mass Series as Indications of
Structural Type ................................. 35
2.5.10 Mass Correlation Table .......................... 37
2.5.11 References ...................................... 45
2.6 UV/Vis Spectroscopy .................................... 46
3 Combination Tables .......................................... 49
3.1 Alkanes, Cycloalkanes .................................. 49
3.2 Alkenes, Cycloalkenes .................................. 50
3.3 Alkynes ................................................ 51
3.4 Aromatic Hydrocarbons .................................. 52
3.5 Heteroaromatic Compounds ............................... 53
3.6 Halogen Compounds ...................................... 54
3.7 Oxygen Compounds ....................................... 56
3.7.1 Alcohols and Phenols ............................ 56
3.7.2 Ethers .......................................... 57
3.8 Nitrogen Compounds ..................................... 59
3.8.1 Amines .......................................... 59
3.8.2 Nitrocompounds .................................. 60
3.9 Thiols and Sulfides .................................... 61
3.10 Carbonyl Compounds ..................................... 62
3.10.1 Aldehydes ....................................... 62
3.10.2 Ketones ......................................... 63
3.10.3 Carboxylic Acids ................................ 64
3.10.4 Esters and Lactones ............................. 65
3.10.5 Amides and Lactams .............................. 67
4 13C NMR Spectroscopy ........................................ 69
4.1 Alkanes ................................................ 69
4.1.1 Chemical Shifts ................................. 69
4.1.2 Coupling Constants .............................. 78
4.1.3 References ...................................... 79
4.2 Alkenes ................................................ 80
4.2.1 Chemical Shifts ................................. 80
4.2.2 Coupling Constants .............................. 84
4.2.3 References ...................................... 84
4.3 Alkynes ................................................ 85
4.3.1 Chemical Shifts ................................. 85
4.3.2 Coupling Constants .............................. 85
4.3.3 References ...................................... 86
4.4 Alicyclics ............................................. 87
4.4.1 Chemical Shifts ................................. 87
4.4.2 Coupling Constants .............................. 92
4.5 Aromatic Hydrocarbons .................................. 93
4.5.1 Chemical Shifts ................................. 93
4.5.2 Coupling Constants ............................. 100
4.5.3 References ..................................... 100
4.6 Heteroaromatic Compounds .............................. 101
4.6.1 Chemical Shifts ................................ 101
4.6.2 Coupling Constants ............................. 108
4.7 Halogen Compounds ..................................... 109
4.7.1 Fluoro Compounds ............................... 109
4.7.2 Chloro Compounds ............................... 1ll
4.7.3 Bromo Compounds ................................ 112
4.7.4 Iodo Compounds ................................. 113
4.7.5 References ..................................... 113
4.8 Alcohols, Ethers, and Related Compounds ............... 114
4.8.1 Alcohols ....................................... 114
4.8.2 Ethers ......................................... 115
4.9 Nitrogen Compounds .................................... 117
4.9.1 Amines ......................................... 117
4.9.2 Nitro and Nitroso Compounds .................... 119
4.9.3 Nitrosamines and Nitramines .................... 120
4.9.4 Azo and Azoxy Compounds ........................ 120
4.9.5 Imines and Oximes .............................. 120
4.9.6 Hydrazones and Carbodiimides ................... 121
4.9.7 Nitriles and Isonitriles ....................... 122
4.9.8 Isocy anates, Thiocyanates, and
Isothiocyanates ................................ 122
4.10 Sulfur Compounds ...................................... 123
4.10.1 Thiols ......................................... 123
4.10.2 Sulfides ....................................... 123
4.10.3 Disulfides and Sulfonium Salts ................. 124
4.10.4 Sulfoxides and Sulfones ........................ 125
4.10.5 Sulfonic and Sulfinic Acids and Derivatives .... 126
4.10.6 Sulfurous and Sulfuric Acid Derivatives ........ 126
4.10.7 Sulfur-Containing Carbonyl Derivatives ......... 127
4.11 Carbonyl Compounds .................................... 128
4.11.1 Aldehydes ...................................... 128
4.11.2 Ketones ........................................ 129
4.11.3 Carboxylic Acids ............................... 131
4.11.4 Esters and Lactones ............................ 133
4.11.5 Amides and Lactams ............................. 135
4.11.6 Miscellaneous Carbonyl Derivatives ............. 137
4.12 Miscellaneous Compounds .............................. 139
4.12.1 Compounds with Group IV Elements ............... 139
4.12.2 Phosphorus Compounds ........................... 140
4.12.3 Miscellaneous Organometallic Compounds ......... 142
4.13 Natural Products ...................................... 144
4.13.1 Amino Acids .................................... 144
4.13.2 Carbohydrates .................................. 148
4.13.3 Nucleotides and Nucleosides .................... 150
4.13.4 Steroids ....................................... 152
4.14 Spectra of Solvents and Reference Compounds ........... 153
4.14.1 13C NMR Spectra of Common Deuterated
Solvents ....................................... 153
4.14.2 13C NMR Spectra of Secondary Reference
Compounds ...................................... 155
4.14.3 13C NMR Spectrum of a Mixture of Common
Nondeuterated Solvents ......................... 156
5 1H NMR Spectroscopy ........................................ 157
5.1 Alkanes ............................................... 157
5.1.1 Chemical Shifts ................................ 157
5.1.2 Coupling Constants ............................. 162
5.2 Alkenes ............................................... 164
5.2.1 Substituted Ethylenes .......................... 164
5.2.2 Conjugated Dienes .............................. 170
5.2.3 Allenes ........................................ 171
5.3 Alkynes ............................................... 172
5.4 Alicyclics ............................................ 173
5.5 Aromatic Hydrocarbons ................................. 177
5.6 Heteroaromatic Compounds .............................. 184
5.6.1 Non-Condensed Heteroaromatic Rings ............. 184
5.6.2 Condensed Heteroaromatic Rings ................. 191
5.7 Halogen Compounds ..................................... 196
5.7.1 Fluoro Compounds ............................... 196
5.7.2 Chloro Compounds ............................... 197
5.7.3 Bromo Compounds ................................ 198
5.7.4 Iodo Compounds ................................. 199
5.8 Alcohols, Ethers, and Related Compounds ............... 200
5.8.1 Alcohols ....................................... 200
5.8.2 Ethers ......................................... 202
5.9 Nitrogen Compounds .................................... 205
5.9.1 Amines ......................................... 205
5.9.2 Nitro and Nitroso Compounds .................... 207
5.9.3 Nitrites and Nitrates .......................... 208
5.9.4 Nitrosamines, Azo and Azoxy Compounds .......... 208
5.9.5 Imines, Oximes,Hydrazones, and Azines .......... 209
5.9.6 Nitriles and Isonitriles ....................... 210
5.9.7 Cyanates, Isocyanates, Thiocyanates, and
Isothiocyanates ................................ 211
5.10 Sulfur Compounds ...................................... 212
5.10.1 Thiols ......................................... 212
5.10.2 Sulfides ....................................... 213
5.10.3 Disulfides and Sulfonium Salts ................. 214
5.10.4 Sulfoxides and Sulfones ........................ 214
5.10.5 Sulfonic, Sulfurous, and Sulfuric Acids and
Derivatives .................................... 215
5.10.6 Thiocarboxylate Derivatives .................... 215
5.11 Carbonyl Compounds .................................... 216
5.11.1 Aldehydes ...................................... 216
5.11.2 Ketones ........................................ 217
5.11.3 Carboxylic Acids and Carboxylates .............. 218
5.11.4 Esters and Lactones ............................ 219
5.11.5 Amides and Lactams ............................. 220
5.11.6 Miscellaneous Carbonyl Derivatives ............. 224
5.12 Miscellaneous Compounds ............................... 226
5.12.1 Compounds with Group IV Elements ............... 226
5.12.2 Phosphorus Compounds ........................... 227
5.12.3 Miscellaneous Compounds ........................ 230
5.12.4 References ..................................... 231
5.13 Natural Products ...................................... 232
5.13.1 Amino Acids .................................... 232
5.13.2 Carbohydrates .................................. 235
5.13.3 Nucleotides and Nucleosides .................... 237
5.14 Spectra of Solvents and Reference Compounds ........... 239
5.14.1 1H NMR Spectra of Common Deuterated Solvents ... 239
5.14.2 1H NMR Spectra of Secondary Reference
Compounds ...................................... 241
5.14.3 1H NMR Spectrum of a Mixture of Common
Nondeuterated Solvents ......................... 242
6 Heteronuclear NMR Spectroscopy .............................. 243
6.1 19F NMR Spectroscopy .................................. 243
6.1.1 19F Chemical Shifts of Perfluoroalkanes ........ 243
6.1.2 Estimation of 19F Chemical Shifts of
Substituted Fluoroethylenes .................... 247
6.1.3 Coupling Constants in Fluorinated Alkanes and
Alkenes ........................................ 248
6.1.4 19F Chemical Shifts of Allenes and Alkynes ..... 249
6.1.5 19F Chemical Shifts and Coupling Constants of
Fluorinated Alicyclics ......................... 250
6.1.6 19F Chemical Shifts and Coupling Constants of
Aromatics and Heteroaromatics .................. 251
6.1.7 19F Chemical Shifts of Alcohols and Ethers ..... 254
6.1.8 19F Chemical Shifts of Fluorinated Amine,
Imine, and Hydroxylamine Derivatives ........... 255
6.1.9 19F Chemical Shifts of Sulfur Compounds ........ 256
6.1.10 19F Chemical Shifts of Carbonyl and
Thiocarbonyl Compounds ......................... 257
6.1.11 19F Chemical Shifts of Fluorinated Boron,
Phosphorus, and Silicon Compounds .............. 258
6.1.12 19F Chemical Shifts of Natural Product
Analogues ...................................... 259
6.1.13 References ..................................... 260
6.2 31PNMR Spectroscopy .................................. 261
6.2.1 31P Chemical Shifts of Tricoordinated
Phosphorus, PR!R2R3 ............................ 261
6.2.2 31P Chemical Shifts of Tetracoordinated
Phosphonium Compounds .......................... 262
6.2.3 31P Chemical Shifts of Compounds with a P=C
or P=N Bond .................................... 263
6.2.4 31P Chemical Shifts of Tetracoordinated P(=0)
and P(=S) Compounds ............................ 264
6.2.5 31P Chemical Shifts of Penta- and
Hexacoordinated Phosphorus Compounds ........... 266
6.2.6 31P Chemical Shifts of Natural Phosphorus
Compounds ...................................... 267
7 IR Spectroscopy ............................................ 269
7.1 Alkanes ............................................... 269
7.2 Alkenes ............................................... 272
7.2.1 Monoenes ....................................... 272
7.2.2 Allenes ........................................ 275
7.3 Alkynes ............................................... 276
7.4 Alicyclics ............................................ 277
7.5 Aromatic Hydrocarbons ................................. 279
7.6 Heteroaromatic Compounds .............................. 282
7.7 Halogen Compounds ..................................... 284
7.7.1 Fluoro Compounds ............................... 284
7.7.2 Chloro Compounds ............................... 285
7.7.3 Bromo Compounds ................................ 286
7.7.4 Iodo Compounds ................................. 286
7.8 Alcohols, Ethers, and Related Compounds ............... 287
7.8.1 Alcohols and Phenols ........................... 287
7.8.2 Ethers, Acetals, and Ketals .................... 288
7.8.3 Epoxides ....................................... 290
7.8.4 Peroxides and Hydroperoxides ................... 291
7.9 Nitrogen Compounds .................................... 292
7.9.1 Amines and Related Compounds ................... 292
7.9.2 Nitro and Nitroso Compounds .................... 294
7.9.3 Imines and Oximes .............................. 296
7.9.4 Azo,Azoxy, and Azothio Compounds ............... 298
7.9.5 Nitriles and Isonitriles ....................... 299
7.9.6 Diazo Compounds ................................ 300
7.9.7 Cyanates and Isocyanates ....................... 301
7.9.8 Thiocyanates and Isothiocyanates ............... 302
7.10 Sulfur Compounds ...................................... 304
7.10.1 Thiols and Sulfides ............................ 304
7.10.2 Sulfoxides and Sulfones ........................ 305
7.10.3 Thiocarbonyl Derivatives ....................... 307
7.10.4 Thiocarbonic Acid Derivatives .................. 307
7.11 Carbonyl Compounds .................................... 310
7.11.1 Aldehydes ...................................... 310
7.11.2 Ketones ........................................ 311
7.11.3 Carboxylic Acids ............................... 314
7.11.4 Esters and Lactones ............................ 316
7.11.5 Amides and Lactams ............................. 319
7.11.6 Acid Anhydrides ................................ 322
7.11.7 AcidHalides .................................... 323
7.11.8 Carbonic Acid Derivatives ...................... 324
7.12 Miscellaneous Compounds .............................. 327
7.12.1 Silicon Compounds .............................. 327
7.12.2 Phosphorus Compounds ........................... 328
7.12.3 Boron Compounds ................................ 331
7.13 Amino Acids ........................................... 332
7.14 Solvents, Suspension Media, and Interferences ......... 333
7.14.1 Infrared Spectra of Common Solvents ............ 333
7.14.2 Infrared Spectra of Suspension Media ........... 334
7.14.3 Interferences in Infrared Spectra .............. 335
8 Mass Spectrometry .......................................... 337
8.1 Alkanes ............................................... 337
8.2 Alkenes ............................................... 339
8.3 Alkynes ............................................... 341
8.4 Alicyclics ............................................ 342
8.5 Aromatic Hydrocarbons ................................. 345
8.6 Heteroaromatic Compounds .............................. 347
8.7 Halogen Compounds ..................................... 352
8.8 Alcohols, Ethers, and Related Compounds ............... 354
8.8.1 Alcohols and Phenols ........................... 354
8.8.2 Hydroperoxides ................................. 356
8.8.3 Ethers ......................................... 356
8.8.4 Aliphatic Epoxides ............................. 359
8.8.5 Aliphatic Peroxides ............................ 360
8.8.6 References ..................................... 361
8.9 Nitrogen Compounds .................................... 362
8.9.1 Amines ......................................... 362
8.9.2 Nitrocompounds ................................. 364
8.9.3 Diazo Compounds and Azobenzenes ................ 364
8.9.4 Azides ......................................... 365
8.9.5 Nitriles and Isonitriles ....................... 366
8.9.6 Cy anates, Isocy anates, Thiocy anates, and
Isothiocyanates ................................ 367
8.9.7 References ..................................... 369
8.10 Sulfur Compounds ...................................... 371
8.10.1 Thiols ......................................... 371
8.10.2 Sulfides and Disulfides ........................ 371
8.10.3 Sulfoxides and Sulfones ........................ 373
8.10.4 Sulfonic Acids and Their Esters and Amides ..... 376
8.10.5 Thiocarboxylic Acid Esters ..................... 377
8.10.6 References ..................................... 378
8.11 Carbonyl Compounds .................................... 379
8.11.1 Aldehydes ...................................... 379
8.11.2 Ketones ........................................ 380
8.11.3 Carboxylic Acids ............................... 381
8.11.4 Carboxylic Acid Anhydrides ..................... 382
8.11.5 Esters and Lactones ............................ 382
8.11.6 Amides and Lactams ............................. 384
8.11.7 Imides ......................................... 386
8.11.8 References ..................................... 387
8.12 Miscellaneous Compounds ............................... 388
8.12.1 Trialkylsilyl Ethers ........................... 388
8.12.2 Phosphorus Compounds ........................... 388
8.12.3 References ..................................... 389
8.13 Mass Spectra of Common Solvents and Matrix
Compounds ............................................. 390
8.13.1 Electron Impact Ionization Mass Spectra of
Common Solvents ................................ 390
8.13.2 Spectra of Common FAB MS Matrix and
Calibration Compounds .......................... 393
8.13.3 Spectra of Common MALDI MS Matrix Compounds .... 398
8.13.4 References ..................................... 400
9 UV/Vis Spectroscopy ........................................ 401
9.1 Correlation between Wavelength of Absorbed Radiation
and Observed Color .................................... 401
9.2 Simple Chromophores ................................... 401
9.3 Conjugated Alkenes .................................... 403
9.3.1 Dienes and Polyenes ............................ 403
9.3.2 α,β-Unsaturated Carbonyl Compounds ............. 404
9.4 Aromatic Hydrocarbons ................................. 406
9.4.1 Monosubstituted Benzenes ....................... 406
9.4.2 Poly substituted Benzenes ...................... 407
9.4.3 Aromatic Carbonyl Compounds .................... 408
9.5 Reference Spectra ..................................... 409
9.5.1 Alkenes and Alkynes ............................ 409
9.5.2 Aromatic Compounds ............................. 410
9.5.3 Heteroaromatic Compounds ....................... 415
9.5.4 Miscellaneous Compounds ........................ 417
9.5.5 Nucleotides .................................... 419
9.6 Common Solvents ....................................... 420
Subject Index ................................................. 421
|
