Spectrometric identification of organic compounds.

Format:

Book

Author/Creator:

Silverstein, Robert M. (Robert Milton), 1916-2007.

Contributor:

Webster, Francis X.

Kiemle, David J.

Classes of 1883 and 1884 Fund.

Language:

English

Subjects (All):

Spectrum analysis--Textbooks.

Spectrum analysis.

Organic compounds--Spectra--Textbooks.

Organic compounds.

Spectrum Analysis.

Chemistry, Organic--methods.

Magnetic Resonance Spectroscopy.

Organic compounds--Spectra.

Medical Subjects:

Spectrum Analysis.

Chemistry, Organic--methods.

Magnetic Resonance Spectroscopy.

Genre:

Textbooks.

Physical Description:

x, 502 pages : illustrations ; 29 cm

Edition:

Seventh edition / Robert M. Silverstein, Francis X. Webster, David J. Kiemle.

Place of Publication:

Hoboken, NJ : John Wiley & Sons, [2005]

Summary:

Originally published in 1962, this was the first book to explore teh identification of organic compounds using spectroscopy. It provides a thorough introduction to the three areas of spectrometry most widely used in spectrometric identification: mass spectrometry, infrared spectrometry, and nuclear magnetic resonance spectrometry. A how-to, hands-on teaching manual with considerably expanded NMR coverage--NMR spectra can now be intrepreted in exquisite detail. This book: · Uses a problem-solving approach with extensive reference charts and tables. · Offers an extensive set of real-data problems offers a challenge to the practicing chemist

Contents:

Chapter 1 Mass Spectrometry 1

1.2 Instrumentation 2

1.3 Ionization Methods 3

1.3.1 Gas-Phase Ionization Methods 3

1.3.1.1 Electron Impact Ionization 3

1.3.1.2 Chemical Ionization 3

1.3.2 Desorption Ionization Methods 4

1.3.2.1 Field Desorption Ionization 4

1.3.2.2 Fast Atom Bombardment Ionization 4

1.3.2.3 Plasma Desorption Ionization 5

1.3.2.4 Laser Desorption Ionization 6

1.3.3 Evaporative Ionization Methods 6

1.3.3.1 Thermospray Mass Spectrometry 6

1.3.3.2 Electrospray Mass Spectrometry 6

1.4 Mass Analyzers 8

1.4.1 Magnetic Spector Mass Spectrometers 9

1.4.2 Quadrupole Mass Spectrometers 10

1.4.3 Ion Trap Mass Spectrometers 10

1.4.4 Time-of-Flight Mass Spectrometer 12

1.4.5 Fourier Transform Mass Spectrometer 12

1.4.6 Tandem Mass Spectrometry 12

1.5 Interpretation of El Mass Spectra 13

1.5.1 Recognition of the Molecular Ion Peak 14

1.5.2 Determination of a Molecular Formula 14

1.5.2.1 Unit-Mass Molecular Ion and Isotope Peaks 14

1.5.2.2 High-Resolution Molecular Ion 15

1.5.3 Use of the Molecular Formula. Index of Hydrogen Deficiency 16

1.5.4 Fragmentation 17

1.5.5 Rearrangements 19

1.6 Mass Spectra of Some Chemical Classes 19

1.6.1 Hydrocarbons 19

1.6.1.1 Saturated Hydrocarbons 19

1.6.1.2 Alkenes (Olefins) 20

1.6.1.3 Aromatic and Aralkyl Hydrocarbons 21

1.6.2 Hydroxy Compounds 22

1.6.2.1 Alcohols 22

1.6.2.2 Phenols 24

1.6.3 Ethers 24

1.6.3.1 Aliphatic Ethers (and Acetals) 24

1.6.3.2 Aromatic Ethers 25

1.6.4 Ketones 26

1.6.4.1 Aliphatic Ketones 26

1.6.4.2 Cyclic Ketones 26

1.6.4.3 Aromatic Ketones 27

1.6.5 Aldehydes 27

1.6.5.1 Aliphatic Aldehydes 27

1.6.5.2 Aromatic Aldehydes 28

1.6.6 Carboxylic Acids 28

1.6.6.1 Aliphatic Acids 28

1.6.6.2 Aromatic Acids 28

1.6.7 Carboxylic Esters 29

1.6.7.1 Aliphatic Esters 29

1.6.7.2 Benzyl and Phenyl Esters 30

1.6.7.3 Esters of Aromatic Acids 30

1.6.8 Lactones 31

1.6.9 Amines 31

1.6.9.1 Aliphatic Amines 31

1.6.9.2 Cyclic Amines 32

1.6.9.3 Aromatic Amines (Anilines) 32

1.6.10 Amides 32

1.6.10.1 Aliphatic Amides 32

1.6.10.2 Aromatic Amides 32

1.6.11 Aliphatic Nitriles 32

1.6.12 Nitro Compounds 33

1.6.12.1 Aliphatic Nitro Compounds 33

1.6.12.2 Aromatic Nitro Compounds 33

1.6.13 Aliphatic Nitrites 33

1.6.14 Aliphatic Nitrates 33

1.6.15 Sulfur Compounds 33

1.6.15.1 Aliphatic Mercaptans (Thiols) 34

1.6.15.2 Aliphatic Sulfides 34

1.6.15.3 Aliphatic Disulfides 35

1.6.16 Halogen Compounds 35

1.6.16.1 Aliphatic Chlorides 36

1.6.16.2 Aliphatic Bromides 37

1.6.16.3 Aliphatic Iodides 37

1.6.16.4 Aliphatic Fluorides 37

1.6.16.5 Benzyl Halides 37

1.6.16.6 Aromatic Halides 37

1.6.17 Heteroaromatic Compounds 37

A Formulas Masses 47

B Common Fragment Ions 68

C Common Fragments Lost 70

Chapter 2 Infrared Spectrometry 72

2.2 Theory 72

2.2.1 Coupled Interaction 75

2.2.2 Hydrogen Bonding 76

2.3 Instrumentation 78

2.3.1 Dispersion IR Spectrometer 78

2.3.2 Fourier Transform Infrared Spectrometer (Interferometer) 78

2.4 Sample Handling 79

2.5 Interpretations of Spectra 80

2.6 Characteristic Group Absorption of Organic Molecules 82

2.6.1 Normal Alkanes (Paraffins) 82

2.6.1.1 C-H Stretching Vibrations 83

2.6.1.2 C-H Bending Vibrations Methyl Groups 83

2.6.2 Branched-Chain Alkanes 84

2.6.2.1 C-H Stretching Vibrations Tertiary C-H Groups 84

2.6.2.2 C-H Bending Vibrations gem-Dimethyl Groups 84

2.6.3 Cyclic Alkanes 85

2.6.3.1 C-H Stretching Vibrations 85

2.6.3.2 C-H Bending Vibrations 85

2.6.4 Alkenes 85

2.6.4.1 C-C Stretching Vibrations Unconjugated Linear Alkenes 85

2.6.4.2 Alkene C-H Stretching Vibrations 86

2.6.4.3 Alkene C-H Bending Vibrations 86

2.6.5 Alkynes 86

2.6.5.1 C-C Stretching Vibrations 86

2.6.5.2 C-H Stretching Vibrations 87

2.6.5.3 C-H Bending Vibrations 87

2.6.6 Mononuclear Aromatic Hydrocarbons 87

2.6.6.1 Out-of-Plane C-H Bending Vibrations 87

2.6.7 Polynuclear Aromatic Hydrocarbons 87

2.6.8 Alcohols and Phenols 88

2.6.8.1 O-H Stretching Vibrations 88

2.6.8.2 C-O Stretching Vibrations 89

2.6.8.3 O-H Bending Vibrations 90

2.6.9 Ethers, Epoxides, and Peroxides 91

2.6.9.1 C-O Stretching Vibrations 91

2.6.10 Ketones 92

2.6.10.1 C-O Stretching Vibrations 92

2.6.10.2 C-C(=O)-C Stretching and Bending Vibrations 94

2.6.11 Aldehydes 94

2.6.11.1 C=O Stretching Vibrations 94

2.6.11.2 C-H Stretching Vibrations 94

2.6.12 Carboxylic Acids 95

2.6.12.1 O-H Stretching Vibrations 95

2.6.12.2 C=O Stretching Vibrations 95

2.6.12.3 C-O Stretching and O-H Bending Vibrations 96

2.6.13 Carboxylate Anion 96

2.6.14 Esters and Lactones 96

2.6.14.1 C=O Stretching Vibrations 97

2.6.14.2 C-O Stretching Vibrations 98

2.6.15 Acid Halides 98

2.6.15.1 C=O Stretching Vibrations 98

2.6.16 Carboxylic Acid Anhydrides 98

2.6.16.1 C=O Stretching Vibrations 98

2.6.16.2 C-O Stretching Vibrations 98

2.6.17 Amides and Lactams 99

2.6.17.1 N-H Stretching Vibrations 99

2.6.17.2 C=O Stretching Vibrations (Amide I Band) 100

2.6.17.3 N-H Bending Vibrations (Amide II Band) 100

2.6.17.4 Other Vibration Bands 101

2.6.17.5 C=O Stretching Vibrations of Lactams 101

2.6.18 Amines 101

2.6.18.1 N-H Stretching Vibrations 101

2.6.18.2 N-H Bending Vibrations 101

2.6.18.3 C-N Stretching Vibrations 102

2.6.19 Amine Salts 102

2.6.19.1 N-H Stretching Vibrations 102

2.6.19.2 N-H Bending Vibrations 102

2.6.20 Amino Acids and Salts of Amino Acids 102

2.6.21 Nitriles 103

2.6.22 Isonitriles (R-N=C), Cyanates (R-O-C=N), Isocyanates (R-N=C=O), Thiocyanates (R-S-C=N), Isothiocyanates (R-N=C=S) 104

2.6.23 Compounds Containing -N=N 104

2.6.24 Covalent Compounds Containing Nitrogen-Oxygen Bonds 104

2.6.24.1 N=O Stretching Vibrations Nitro Compounds 104

2.6.25 Organic Sulfur Compounds 105

2.6.25.1 S=H Stretching Vibrations Mercaptans 105

2.6.25.2 C-S and C=S Stretching Vibrations 106

2.6.26 Compounds Containing Sulfur-Oxygen Bonds 106

2.6.26.1 S=O Stretching Vibrations Sulfoxides 106

2.6.27 Organic Halogen Compounds 107

2.6.28 Silicon Compounds 107

2.6.28.1 Si-H Vibrations 107

2.6.28.2 SiO-H and Si-O Vibrations 107

2.6.28.3 Silicon-Halogen Stretching Vibrations 107

2.6.29 Phosphorus Compounds 107

2.6.29.1 P=O and P-O Stretching Vibrations 107

2.6.30 Heteroaromatic Compounds 107

2.6.30.1 C-H Stretching Vibrations 107

2.6.30.2 N-H Stretching Frequencies 108

2.6.30.3 Ring Stretching Vibrations (Skeletal Bands) 108

2.6.30.4 C-H Out-of-Plane Bending 108

A Transparent Regions of Solvents and Mulling Oils 119

B Characteristic Group Absorptions 120

C Absorptions for Alkenes 125

D Absorptions for Phosphorus Compounds 126

E Absorptions for Heteroaromatics 126

Chapter 3 Proton Magnetic Resonance Spectrometry 127

3.2 Theory 127

3.2.1 Magnetic Properties of Nuclei 127

3.2.2 Excitation of Spin 1/2 Nuclei 128

3.2.3 Relaxation 130

3.3 Instrumentation and Sample Handling 135

3.3.1 Instrumentation 135

3.3.2 Sensitivity of NMR Experiments 136

3.3.3 Solvent Selection 137

3.4 Chemical Shift 137

3.5 Spin Coupling, Multiplets, Spin Systems 143

3.5.1 Simple and Complex First Order Multiplets 145

3.5.2 First Order Spin Systems 146

3.5.3 Pople Notions 147

3.5.4 Further Examples of Simple, First-Order Spin Systems 147

3.5.5 Analysis of First-Order Patterns 148

3.6 Protons on Oxygen, Nitrogen, and Sulfur Atoms.

Exchangeable Protons 160

3.6.1 Protons on an Oxygen Atom 150

3.6.1.1 Alcohols 150

3.6.1.2 Water 153

3.6.1.3 Phenols 153

3.6.1.4 Enols 153

3.6.1.5 Carboxylic Acids 153

3.6.2 Protons on Nitrogen 153

3.6.3 Protons on Sulfur 155

3.6.4 Protons on or near Chlorine, Bromine, or Iodine Nuclei 155

3.7 Coupling of Protons to Other Important Nuclei ([superscript 19]F, D, [superscript 31]P, [superscript 29]Si, and [superscript 13]C) 155

3.7.1 Coupling of Protons to [superscript 19]F 155

3.7.2 Coupling of Protons to D 155

3.7.3 Coupling of Protons to [superscript 31]P 156

3.7.4 Coupling of Protons to [superscript 29]Si 156

3.7.5 Coupling of Protons to [superscript 13]C 156

3.8 Chemical Shift Equivalence 157

3.8.1 Determination of Chemical Shift Equivalence by Interchange Through Symmetry Operations 157

3.8.1.1 Interchange by Rotation Around a Simple Axis of Symmetry (C[subscript n]) 157

3.8.1.2 Interchange by Reflection Through a Plane of Symmetry ([sigma]) 157

3.8.1.3 Interchange by Inversion Through a Center of Symmetry (i) 158

3.8.1.4 No Interchangeability by a Symmetry Operations 158

3.8.2 Determination of Chemical Shift Equivalence by Tagging (or Substitution) 159

3.8.3 Chemical Shift Equivalence by Rapid Interconversion of Structures 160

3.8.3.1 Keto-Enol Interconversion 160

3.8.3.2 Interconversion Around a "Partial Double Bond" (Restricted Rotation) 160

3.8.3.3 Interconversion Around the Single Bond of Rings 160

3.8.3.4 Interconversion Around the Single Bonds of Chains 161

3.9 Magnetic Equivalence (Spin-Coupling Equivalence) 162

3.10 AMX, ABX, and ABC Rigid Systems with Three Coupling Constants 164

3.11 Confirmationally Mobile, Open-Chain Systems. Virtual Coupling 165

3.11.1 Unsymmetrical Chains 165

3.11.1.1 1-Nitropropane 165

3.11.1.2 1-Hexanol 165

3.11.2 Symmetrical Chains 167

3.11.2.1 Dimethyl Succinate 167

3.11.2.2 Dimethyl Glutarate 167

3.11.2.3 Dimethyl Adipate 167

3.11.2.4 Dimethyl Pimelate 168

3.11.3 Less Symmetrical Chains 168

3.11.3.1 3-Methylglutaric Acid 168

3.12 Chirality 169

3.12.1 One Chiral Center, Ipsenol 169

3.12.2 Two Chiral Centers 171

3.13 Vicinal and Geminal Coupling 171

3.14 Low-Range Coupling 172

3.15 Selective Spin Decoupling. Double Resonance 173

3.16 Nuclear Overhauser Effect, Difference Spectrometry, 1H 1H Proximity Through Space 173

A Chemicals Shifts of a Proton 188

B Effect on Chemical Shifts by Two or Three Directly Attached Functional Groups 191

C Chemical Shifts in Alicyclic and Heterocyclic Rings 193

D Chemical Shifts in Unsaturated and Aromatic Systems 194

E Protons on Heteroatoms 197

F Proton Spin-Coupling Constants 198

G Chemical Shifts and Multiplicities of Residual Protons in Commercially Available Deuterated Solvents 200

H [superscript 1]H NMR Data 201

I Proton NMR Chemical Shifts of Amino Acids in D[subscript 2]O 203

Chapter 4 Carbon-13 NMR Spectrometry 204

4.2 Theory 204

4.2.1 [superscript 1]H Decoupling Techniques 204

4.2.2 Chemical Shift Scale and Range 205

4.2.3 T[subscript 1] Relaxation 206

4.2.4 Nuclear Overhauser Enhancement (NOE) 207

4.2.5 [superscript 13]C-[superscript 1]H Sping Coupling (J Values) 209

4.2.6 Sensitivity 210

4.2.7 Solvents 210

4.3 Interpretation of a Simple [superscript 13]C Spectrum: Diethyl Phthalate 211

4.4 Quantitative [superscript 13]C Analysis 213

4.5 Chemical Shift Equivalence 214

4.6 Dept 215

4.7 Chemical Classes and Chemical Shifts 217

4.7.1 Alkanes 218

4.7.1.1 Linear and Branched Alkanes 218

4.7.1.2 Effect of Substituents on Alkenes 218

4.7.1.3 Cycloalkanes and Saturated Heterocyclics 220

4.7.2 Alkenes 220

4.7.3 Alkynes 221

4.7.4 Aromatic Compounds 222

4.7.5 Heteroaromatic Compounds 223

4.7.6 Alcohols 223

4.7.7 Ethers, Acetals, and Epoxides 225

4.7.8 Halides 225

4.7.9 Amines 226

4.7.10 Thiols, Sulfides, and Disulfides 226

4.7.11 Functional Groups Containing Carbon 226

4.7.11.1 Ketones and Aldehydes 227

4.7.11.2 Carboxylic Acids, Esters, Chlorides, Anhydrides, Amides, and Nitriles 227

4.7.11.3 Oximes 227

A The [superscript 13]C Chemical Shifts, Couplings and Multiplicities of Common NMR Solvents 240

B [superscript 13]C Chemical Shift for Common Organic Compounds in Different Solvents 241

C The [superscript 13]C Correlation Chart for Chemical Classes 242

D [superscript 13]C NMR Data for Several Natural Products ([delta]) 244

Chapter 5 Correlation NMR Spectrometry; 2-D NMR 245

5.2 Theory 246

5.3 Correlation Spectrometry 249

5.3.1 [superscript 1]H-[superscript 1]H Correlation: COSY 250

5.4 Ipsenol: [superscript 1]H-[superscript 1]H COSY 251

5.4.1 Ipsenol: Double Quantum Filtered [superscript 1]H-[superscript 1]H COSY 251

5.4.2 Carbon Detected 13C-1H COSY: HECTOR 254

5.4.3 Proton Detected [superscript 1]H-[superscript 13]C COSY: HMQC 254

5.4.4 Ipsenol: HECTOR and HMQC 255

5.4.5 Ipsenol: Proton-Detected, Long Range [superscript 1]H-[superscript 13]C Heteronuclear Correlation: HMBC 257

5.5 Caryophyllene Oxide 259

5.5.1 Caryophyllene Oxide: DQF-COSY 259

5.5.2 Caryophyllene Oxide: HMQC 259

5.5.3 Caryophyllene Oxide: HMBC 263

5.6 [superscript 13]C-[superscript 13]C Correlations: Inadequate 265

5.6.1 Inadequate: Caryophyllene Oxide 266

5.7 Lactose 267

5.7.1 DQF-COSY: Lactose 267

5.7.2 HMQC: Lactose 270

5.7.3 HMBC: Lactose 270

5.8 Relayed Coherence Transfer: TOCSY 270

5.8.1 2-D TOCSY: Lactose 270

5.8.2 1-D TOCSY: Lactose 273

5.9 HMQC - TOCSY 275

5.9.1 HMQC - TOCSY: Lactose 275

5.10 ROESY 275

5.10.1 ROESY: Lactose 275

5.11 VGSE 278

5.11.1 COSY: VGSE 278

5.11.2 TOCSY: VGSE 278

5.11.3 HMQC: VGSE 278

5.11.4 HMBC: VGSE 281

5.11.5 ROESY: VGSE 282

5.12 Gradient Field NMR 282

Chapter 6 Nmr Spectrometry of Other Important Spin 1/2 Nuclei 316

6.2 [superscript 15]N Nuclear Magnetic Resonance 317

6.3 [superscript 19]F Nuclear Magnetic Resonance 323

6.4 [superscript 29]Si Nuclear Magnetic Resonance 326

6.5 [superscript 31]P Nuclear Magnetic Resonance 327

A Properties of Magnetically Active Nuclei 338

Chapter 7 Solved Problems 341

Problem 7.1 Discussion 345

Problem 7.2 Discussion 349

Problem 7.3 Discussion 353

Problem 7.4 Discussion 360

Problem 7.5 Discussion 367

Problem 7.6 Discussion 373

Chapter 8 Assigned Problems 381.

Notes:

Includes index.

Local Notes:

Acquired for the Penn Libraries with assistance from the Classes of 1883 and 1884 Fund.

ISBN:

0471393622

0471429139

OCLC:

58546559