Spectrometric Identification of Organic Compounds

Robert M. Silverstein, PhD was as born in Baltimore, MD, and moved to Staten Island at a young age. He received his bachelor's degree from the University of Pennsylvania in 1937 and his masters' degree from New York University in 1941. He served with the U.S. Army during World War II. He then earned his doctorate from New York University.Francis X. Webster is the author of Spectrometric Identification of Organic Compounds, 8th Edition, published by Wiley.David J. Kiemle is the author of Spectrometric Identification of Organic Compounds, 8th Edition, published by Wiley.David L. Bryce is the author of Spectrometric Identification of Organic Compounds, 8th Edition, published by Wiley.

• CHAPTER 1 MASS SPECTROMETRY 11.1 Introduction 11.2 Instrumentation 21.3 Ionization Methods 31.4 Mass Analyzers 81.5 Interpretation of EI Mass Spectra 121.6 Mass Spectra of Some Chemical Classes 18References 37Student Exercises 37Appendices 46A Formula Masses (FM) for Various Combinations of Carbon, Hydrogen, Nitrogen, and Oxygen 46B Common Fragment Ions 67C Common Fragments Lost 69CHAPTER 2 INFRARED SPECTROSCOPY 712.1 Introduction 712.2 Theory 712.3 Instrumentation 762.4 Sample Handling 772.5 Interpretation of Spectra 782.6 Characteristic Group Absorptions of Organic Molecules 81References 108Student Exercises 108Appendices 118A Transparent Regions of Solvents and Mulling Oils 118B Characteristic Group Absorptions 119C Absorptions for Alkenes 124D Absorptions for Phosphorus Compounds 125E Absorptions for Heteroaromatics 125CHAPTER 3 PROTON (1H) MAGNETIC RESONANCE SPECTROSCOPY 1263.1 Introduction 1263.2 Theory 1263.3 Instrumentation and Sample Handling 1293.4 Chemical Shift 1323.5 Spin-Spin Coupling, Multiplets, and Spin Systems 1373.6 Protons on Oxygen, Nitrogen, and Sulfur Atoms:Exchangeable Protons 1443.7 Coupling of Protons to Other Important Nuclei (19F, D (2H), 31P, 29Si, and 13C) 1493.8 Chemical Equivalence 1503.9 Magnetic Equivalence 1543.10 AMX, ABX, and ABC Rigid Systems with Three Coupling Constants 1553.11 Weakly and Strongly Coupled Systems: Virtual Coupling 1563.12 Chirality 1583.13 Magnitude of Vicinal and Geminal Coupling Constants 1603.14 Long-Range Coupling 1623.15 Selective Spin Decoupling: Double Resonance 1623.16 Nuclear Overhauser Effect 1623.17 Conclusion 163References 164Student Exercises 164Appendices 175A Chart A.1: Chemical Shifts of Protons on a Carbon Atom Adjacent (𝛼 Position) to a Functional Group in Aliphatic Compounds (M–Y) 175Chart A.2: Chemical Shifts of Protons on a Carbon Atom Once Removed (𝛽 Position) from a Functional Group in Aliphatic Compounds (M–C–Y) 177B Effect on Chemical Shifts by Two or Three Directly Attached Functional Groups 178C Chemical Shifts in Alicyclic and Heterocyclic Rings 180D Chemical Shifts in Unsaturated and Aromatic Systems 181Chart D.1: Chemical Shifts of Protons on Monosubstituted Benzene Rings 183E Protons Subject to Hydrogen-Bonding Effects (Protons on Heteroatoms) 184F Proton Spin-Spin Coupling Constants 185G Chemical Shifts and Multiplicities of Residual Protons in Commercially Available Deuterated Solvents 187H Chemical Shifts of Common Laboratory Solvents as Trace Impurities 188I Proton NMR Chemical Shifts of Amino Acids in D2O 190CHAPTER 4 CARBON-13 NMR SPECTROSCOPY 1914.1 Introduction 1914.2 Theory 1914.3 Interpretation of a Simple 13C NMR Spectrum: Diethyl Phthalate 1984.4 Quantitative 13C Analysis 1984.5 Chemical Equivalence 2004.6 DEPT 2004.7 Chemical Classes and Chemical Shifts 2034.7.1 Alkanes 2044.7.1.1 Linear and Branched Alkanes 2044.7.1.2 Effect of Substituents on Alkanes 2054.7.1.3 Cycloalkanes and Saturated Heterocyclics 2054.7.2 Alkenes 2064.7.3 Alkynes 2084.7.4 Aromatic Compounds 2084.7.5 Heteroaromatic Compounds 2094.7.6 Alcohols 2094.7.7 Ethers, Acetals, and Epoxides 2094.7.8 Halides 2114.7.9 Amines 2114.7.10 Thiols, Sulfides, and Disulfides 2114.7.11 Functional Groups Containing Carbon 2114.7.11.1 Ketones and Aldehydes 2124.7.11.2 Carboxylic Acids, Esters, Chlorides, Anhydrides, Amides, and Nitriles 2144.7.11.3 Oximes 214References 214Student Exercises 214Appendices 225A The 13C Chemical Shifts, Coupling Constants, and Peak Multiplicities of Common Deuterated NMR Solvents 225B 13C Chemical Shifts of Common Laboratory Solvents as Trace Impurities in Selected Deuterated NMR Solvents 226C 13C Chemical Shift Ranges for Chemical Classes 227D 13C Chemical Shifts (ppm) for Several Natural Products 229CHAPTER 5 TWO-DIMENSIONAL NMR SPECTROSCOPY 2305.1 Introduction 2305.2 Theory 2315.3 Correlation Spectroscopy 2335.3.1 1H-1H Correlation: COSY 2355.4 Ipsenol: 1H-1H COSY 2355.4.1 Ipsenol: Double Quantum Filtered 1H-1H COSY 2385.4.2 Carbon Detected 13C-1H COSY: HETCOR 2385.4.3 Proton Detected 1H-13C COSY: HMQC 2395.4.4 Ipsenol: HETCOR and HMQC 2395.4.5 Ipsenol: Proton-Detected, Long-Range 1H-13C Heteronuclear Correlation: HMBC 2415.5 Caryophyllene Oxide 2435.5.1 Caryophyllene Oxide: DQF-COSY 2435.5.2 Caryophyllene Oxide: HMQC 2435.5.3 Caryophyllene Oxide: HMBC 2475.6 13C-13C Correlations: INADEQUATE 2495.6.1 INADEQUATE: Caryophyllene Oxide 2515.7 Lactose 2515.7.1 DQF-COSY: Lactose 2515.7.2 HMQC: Lactose 2545.7.3 HMBC: Lactose 2545.8 Relayed Coherence Transfer: TOCSY 2545.8.1 2D TOCSY: Lactose 2545.8.2 1D TOCSY: Lactose 2575.9 HMQC-TOCSY 2595.9.1 HMQC-TOCSY: Lactose 2595.10 ROESY 2595.10.1 ROESY: Lactose 2595.11 VGSE 2625.11.1 COSY: VGSE 2625.11.2 TOCSY: VGSE 2625.11.3 HMQC: VGSE 2625.11.4 HMBC: VGSE 2645.11.5 ROESY: VGSE 2655.12 Pulsed Field Gradient NMR 265References 268Student Exercises 268CHAPTER 6 MULTINUCLEAR MAGNETIC RESONANCE SPECTROSCOPY 2986.1 Introduction and General Considerations 2986.2 15N Nuclear Magnetic Resonance 2996.3 19F Nuclear Magnetic Resonance 3066.4 29Si Nuclear Magnetic Resonance 3096.5 31P Nuclear Magnetic Resonance 3126.6 Conclusions 315References 315Student Exercises 315Appendix 320A Properties of Magnetically Active Nuclei 320CHAPTER 7 SOLVED PROBLEMS 3257.1 Introduction 325Problem 7.1 Discussion 329Problem 7.2 Discussion 333Problem 7.3 Discussion 337Problem 7.4 Discussion 344Problem 7.5 Discussion 350Problem 7.6 Discussion 356Student Exercises 357CHAPTER 8 ASSIGNED PROBLEMS 3648.1 Introduction 364INDEX 453