L. D. Field, Professor of Chemistry, School of Chemistry, University of New South Wales, Australia H. L. Li, Senior Research Associate, School of Chemistry, University of New South Wales, Australia A. M. Magill, Honorary Associate, School of Chemistry, University of New South Wales, Australia

• Preface ixList of Tables xiiiList of Figures xv1 Introduction 11.1 General Principles of Absorption Spectroscopy 11.2 Chromophores 21.3 Degree of Unsaturation 31.4 Connectivity 41.5 Sensitivity 41.6 Practical Considerations 52 Ultraviolet (UV) Spectroscopy 62.1 The Nature of Ultraviolet Spectroscopy 62.2 Basic Instrumentation 62.3 Quantitative Aspects of Ultraviolet Spectroscopy 82.4 Classification of UV Absorption Bands 82.5 Special Terms in Ultraviolet Spectroscopy 92.6 Important UV Chromophores 102.6.1 Dienes and Polyenes 102.6.2 Carbonyl Compounds 112.6.3 Benzene Derivatives 112.7 The Effect of Solvents 133 Infrared (IR) Spectroscopy 143.1 Absorption Range and the Nature of IR Absorption 143.2 Experimental Aspects of Infrared Spectroscopy 153.3 General Features of Infrared Spectra 163.4 Important IR Chromophores 183.4.1 –O–H and –N–H Stretching Vibrations 183.4.2 C–H Stretching Vibrations 183.4.3 –C≡N and –C≡C– Stretching Vibrations 193.4.4 Carbonyl Groups 193.4.5 Other Polar Functional Groups 213.4.6 The Fingerprint Region 214 Mass Spectrometry 234.1 Ionisation Processes 234.2 Instrumentation 254.3 Mass Spectral Data 264.3.1 High Resolution Mass Spectra 264.3.2 Molecular Fragmentation 284.3.3 Isotope Ratios 294.3.4 Chromatography Coupled With Mass Spectrometry 314.3.5 Metastable Peaks 314.4 Representation of Fragmentation Processes 314.5 Factors Governing Fragmentation Processes 324.6 Examples of Common Types of Fragmentation 324.6.1 Cleavage at Branch Points 324.6.2 Β-Cleavage 334.6.3 Cleavage Α to Carbonyl Groups 334.6.4 Cleavage Α to Heteroatoms 344.6.5 Retro Diels–Alder Reaction 344.6.6 The Mclafferty Rearrangement 345 1H Nuclear Magnetic Resonance (NMR) Spectroscopy 365.1 The Physics of Nuclear Spins and NMR Instruments 365.1.1 The Larmor Equation and Nuclear Magnetic Resonance 365.2 Basic NMR Instrumentation 395.2.1 CW and Pulsed NMR Spectrometers 395.2.2 Nuclear Relaxation 425.2.3 Magnets for NMR Spectroscopy 435.2.4 The NMR Spectrum 445.3 Chemical Shift in 1H NMR Spectroscopy 455.4 Spin–Spin Coupling in 1H NMR Spectroscopy 525.4.1 Signal Multiplicity – The N+1 Rule 545.5 Analysis of 1H NMR Spectra 555.5.1 Spin Systems 565.5.2 Strongly and Weakly Coupled Spin Systems 565.5.3 Magnetic Equivalence 585.5.4 Conventions for Naming Spin Systems 595.5.5 Spectral Analysis of First-Order NMR Spectra 605.5.6 Splitting Diagrams 615.5.7 Spin Decoupling 645.6 Correlation of 1H–1H Coupling With Structure 655.6.1 Non-Aromatic Spin Systems 655.6.2 Aromatic Spin Systems 665.7 The Nuclear Overhauser Effect (NOE) 695.8 Labile and Exchangeable Protons 706 13c NMR Spectroscopy 726.1 Coupling and Decoupling in 13c NMR Spectra 726.2 The Nuclear Overhauser Effect (NOE) in 13c NMR Spectroscopy 736.3 Determining 13c Signal Multiplicity Using Dept 736.4 Shielding and Characteristic Chemical Shifts in 13c NMR Spectra 767 2-Dimensional NMR Spectroscopy 827.1 Proton–Proton Interactions By 2D NMR 857.1.1 COSY (Correlation Spectroscopy) 857.1.2 TOCSY (Total Correlation Spectroscopy) 867.1.3 NOESY (Nuclear Overhauser Effect Spectroscopy) 887.2 Proton–Carbon Interactions By 2D NMR 897.2.1 The HSQC (Heteronuclear Single Quantum Correlation) or HSC (Heteronuclear Shift Correlation) Spectrum 897.2.2 HMBC (Heteronuclear Multiple Bond Correlation) 918 Miscellaneous Topics 968.1 Solvents for NMR Spectroscopy 968.2 Solvent-Induced Shifts 978.3 Dynamic Processes in NMR – The NMR Time-Scale 988.3.1 Conformational Exchange Processes 998.3.2 Intermolecular Exchange of Labile Protons 998.3.3 Rotation About Partial Double Bonds 1008.4 The Effect of Chirality 1008.5 The NMR Spectra of “Other Nuclei” 1019 Determining the Structure of Organic Compounds From Spectra 1029.1 Solving Problems 1039.2 Worked Examples 10410 Problems 115Index 538

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L. D. Field, Professor of Chemistry, School of Chemistry, University of New South Wales, Australia H. L. Li, Senior Research Associate, School of Chemistry, University of New South Wales, Australia A. M. Magill, Honorary Associate, School of Chemistry, University of New South Wales, Australia

• Preface ixList of Tables xiiiList of Figures xv1 Introduction 11.1 General Principles of Absorption Spectroscopy 11.2 Chromophores 21.3 Degree of Unsaturation 31.4 Connectivity 41.5 Sensitivity 41.6 Practical Considerations 52 Ultraviolet (UV) Spectroscopy 62.1 The Nature of Ultraviolet Spectroscopy 62.2 Basic Instrumentation 62.3 Quantitative Aspects of Ultraviolet Spectroscopy 82.4 Classification of UV Absorption Bands 82.5 Special Terms in Ultraviolet Spectroscopy 92.6 Important UV Chromophores 102.6.1 Dienes and Polyenes 102.6.2 Carbonyl Compounds 112.6.3 Benzene Derivatives 112.7 The Effect of Solvents 133 Infrared (IR) Spectroscopy 143.1 Absorption Range and the Nature of IR Absorption 143.2 Experimental Aspects of Infrared Spectroscopy 153.3 General Features of Infrared Spectra 163.4 Important IR Chromophores 183.4.1 –O–H and –N–H Stretching Vibrations 183.4.2 C–H Stretching Vibrations 183.4.3 –C≡N and –C≡C– Stretching Vibrations 193.4.4 Carbonyl Groups 193.4.5 Other Polar Functional Groups 213.4.6 The Fingerprint Region 214 Mass Spectrometry 234.1 Ionisation Processes 234.2 Instrumentation 254.3 Mass Spectral Data 264.3.1 High Resolution Mass Spectra 264.3.2 Molecular Fragmentation 284.3.3 Isotope Ratios 294.3.4 Chromatography Coupled With Mass Spectrometry 314.3.5 Metastable Peaks 314.4 Representation of Fragmentation Processes 314.5 Factors Governing Fragmentation Processes 324.6 Examples of Common Types of Fragmentation 324.6.1 Cleavage at Branch Points 324.6.2 Β-Cleavage 334.6.3 Cleavage Α to Carbonyl Groups 334.6.4 Cleavage Α to Heteroatoms 344.6.5 Retro Diels–Alder Reaction 344.6.6 The Mclafferty Rearrangement 345 1H Nuclear Magnetic Resonance (NMR) Spectroscopy 365.1 The Physics of Nuclear Spins and NMR Instruments 365.1.1 The Larmor Equation and Nuclear Magnetic Resonance 365.2 Basic NMR Instrumentation 395.2.1 CW and Pulsed NMR Spectrometers 395.2.2 Nuclear Relaxation 425.2.3 Magnets for NMR Spectroscopy 435.2.4 The NMR Spectrum 445.3 Chemical Shift in 1H NMR Spectroscopy 455.4 Spin–Spin Coupling in 1H NMR Spectroscopy 525.4.1 Signal Multiplicity – The N+1 Rule 545.5 Analysis of 1H NMR Spectra 555.5.1 Spin Systems 565.5.2 Strongly and Weakly Coupled Spin Systems 565.5.3 Magnetic Equivalence 585.5.4 Conventions for Naming Spin Systems 595.5.5 Spectral Analysis of First-Order NMR Spectra 605.5.6 Splitting Diagrams 615.5.7 Spin Decoupling 645.6 Correlation of 1H–1H Coupling With Structure 655.6.1 Non-Aromatic Spin Systems 655.6.2 Aromatic Spin Systems 665.7 The Nuclear Overhauser Effect (NOE) 695.8 Labile and Exchangeable Protons 706 13c NMR Spectroscopy 726.1 Coupling and Decoupling in 13c NMR Spectra 726.2 The Nuclear Overhauser Effect (NOE) in 13c NMR Spectroscopy 736.3 Determining 13c Signal Multiplicity Using Dept 736.4 Shielding and Characteristic Chemical Shifts in 13c NMR Spectra 767 2-Dimensional NMR Spectroscopy 827.1 Proton–Proton Interactions By 2D NMR 857.1.1 COSY (Correlation Spectroscopy) 857.1.2 TOCSY (Total Correlation Spectroscopy) 867.1.3 NOESY (Nuclear Overhauser Effect Spectroscopy) 887.2 Proton–Carbon Interactions By 2D NMR 897.2.1 The HSQC (Heteronuclear Single Quantum Correlation) or HSC (Heteronuclear Shift Correlation) Spectrum 897.2.2 HMBC (Heteronuclear Multiple Bond Correlation) 918 Miscellaneous Topics 968.1 Solvents for NMR Spectroscopy 968.2 Solvent-Induced Shifts 978.3 Dynamic Processes in NMR – The NMR Time-Scale 988.3.1 Conformational Exchange Processes 998.3.2 Intermolecular Exchange of Labile Protons 998.3.3 Rotation About Partial Double Bonds 1008.4 The Effect of Chirality 1008.5 The NMR Spectra of “Other Nuclei” 1019 Determining the Structure of Organic Compounds From Spectra 1029.1 Solving Problems 1039.2 Worked Examples 10410 Problems 115Index 538

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L. D. Field, Professor of Chemistry, School of Chemistry, University of New South Wales, Australia H. L. Li, Senior Research Associate, School of Chemistry, University of New South Wales, Australia A. M. Magill, Honorary Associate, School of Chemistry, University of New South Wales, Australia

• Preface ixList of Tables xiiiList of Figures xv1 Introduction 11.1 General Principles of Absorption Spectroscopy 11.2 Chromophores 21.3 Degree of Unsaturation 31.4 Connectivity 41.5 Sensitivity 41.6 Practical Considerations 52 Ultraviolet (UV) Spectroscopy 62.1 The Nature of Ultraviolet Spectroscopy 62.2 Basic Instrumentation 62.3 Quantitative Aspects of Ultraviolet Spectroscopy 82.4 Classification of UV Absorption Bands 82.5 Special Terms in Ultraviolet Spectroscopy 92.6 Important UV Chromophores 102.6.1 Dienes and Polyenes 102.6.2 Carbonyl Compounds 112.6.3 Benzene Derivatives 112.7 The Effect of Solvents 133 Infrared (IR) Spectroscopy 143.1 Absorption Range and the Nature of IR Absorption 143.2 Experimental Aspects of Infrared Spectroscopy 153.3 General Features of Infrared Spectra 163.4 Important IR Chromophores 183.4.1 –O–H and –N–H Stretching Vibrations 183.4.2 C–H Stretching Vibrations 183.4.3 –C≡N and –C≡C– Stretching Vibrations 193.4.4 Carbonyl Groups 193.4.5 Other Polar Functional Groups 213.4.6 The Fingerprint Region 214 Mass Spectrometry 234.1 Ionisation Processes 234.2 Instrumentation 254.3 Mass Spectral Data 264.3.1 High Resolution Mass Spectra 264.3.2 Molecular Fragmentation 284.3.3 Isotope Ratios 294.3.4 Chromatography Coupled With Mass Spectrometry 314.3.5 Metastable Peaks 314.4 Representation of Fragmentation Processes 314.5 Factors Governing Fragmentation Processes 324.6 Examples of Common Types of Fragmentation 324.6.1 Cleavage at Branch Points 324.6.2 Β-Cleavage 334.6.3 Cleavage Α to Carbonyl Groups 334.6.4 Cleavage Α to Heteroatoms 344.6.5 Retro Diels–Alder Reaction 344.6.6 The Mclafferty Rearrangement 345 1H Nuclear Magnetic Resonance (NMR) Spectroscopy 365.1 The Physics of Nuclear Spins and NMR Instruments 365.1.1 The Larmor Equation and Nuclear Magnetic Resonance 365.2 Basic NMR Instrumentation 395.2.1 CW and Pulsed NMR Spectrometers 395.2.2 Nuclear Relaxation 425.2.3 Magnets for NMR Spectroscopy 435.2.4 The NMR Spectrum 445.3 Chemical Shift in 1H NMR Spectroscopy 455.4 Spin–Spin Coupling in 1H NMR Spectroscopy 525.4.1 Signal Multiplicity – The N+1 Rule 545.5 Analysis of 1H NMR Spectra 555.5.1 Spin Systems 565.5.2 Strongly and Weakly Coupled Spin Systems 565.5.3 Magnetic Equivalence 585.5.4 Conventions for Naming Spin Systems 595.5.5 Spectral Analysis of First-Order NMR Spectra 605.5.6 Splitting Diagrams 615.5.7 Spin Decoupling 645.6 Correlation of 1H–1H Coupling With Structure 655.6.1 Non-Aromatic Spin Systems 655.6.2 Aromatic Spin Systems 665.7 The Nuclear Overhauser Effect (NOE) 695.8 Labile and Exchangeable Protons 706 13c NMR Spectroscopy 726.1 Coupling and Decoupling in 13c NMR Spectra 726.2 The Nuclear Overhauser Effect (NOE) in 13c NMR Spectroscopy 736.3 Determining 13c Signal Multiplicity Using Dept 736.4 Shielding and Characteristic Chemical Shifts in 13c NMR Spectra 767 2-Dimensional NMR Spectroscopy 827.1 Proton–Proton Interactions By 2D NMR 857.1.1 COSY (Correlation Spectroscopy) 857.1.2 TOCSY (Total Correlation Spectroscopy) 867.1.3 NOESY (Nuclear Overhauser Effect Spectroscopy) 887.2 Proton–Carbon Interactions By 2D NMR 897.2.1 The HSQC (Heteronuclear Single Quantum Correlation) or HSC (Heteronuclear Shift Correlation) Spectrum 897.2.2 HMBC (Heteronuclear Multiple Bond Correlation) 918 Miscellaneous Topics 968.1 Solvents for NMR Spectroscopy 968.2 Solvent-Induced Shifts 978.3 Dynamic Processes in NMR – The NMR Time-Scale 988.3.1 Conformational Exchange Processes 998.3.2 Intermolecular Exchange of Labile Protons 998.3.3 Rotation About Partial Double Bonds 1008.4 The Effect of Chirality 1008.5 The NMR Spectra of “Other Nuclei” 1019 Determining the Structure of Organic Compounds From Spectra 1029.1 Solving Problems 1039.2 Worked Examples 10410 Problems 115Index 538

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