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Chapter 1 Introduction of Spectroscopy1

1.1Introduction of Electromagnetic Radiation1

1.1.1Electromagnetic Spectrum1

1.1.2Interaction with Electromagnetic Wave3

1.1.3Wavelength£¨λ£©£¬Frequency£¨ν£©and Energy£¨E£©5

1.2Major Spectroscopic Techniques6

1.2.1Absorption Spectrum6

1.2.2Diffraction6

1.2.3Molecular and Fragment Spectrum6

References8

Problems8



Chapter 2 Ultraviolet and Visible Spectroscopy10

2.1Introductions of Ultraviolet and Visible Spectroscopy10

2.2Principles of Ultraviolet and Visible Spectroscopy11

2.3Presentation of Ultraviolet and Visible Spectrum13

2.4Terms Describing UV Absorptions14

2.5Classification of Adsorption Bands16

2.6The Main Influencing Factors of the Maximum Wavelength17

2.6.1Conjugation Effect17

2.6.2Steric Effect19

2.6.3The Polarity of the Solvent20

2.6.4The pH of the Solution21

2.7Solvent21

2.8Relationship Between Molecular Structure and UV Spectrum22

2.8.1Saturated Hydrocarbon Compounds22

2.8.2The Simplest Unsaturated Compounds23

2.8.3The Conjugated Alkenes24

2.8.4The Conjugated Unsaturated Carbonyl Compounds25

2.8.5Aromatic Compounds27

2.9Application of UV Spectroscopy30

2.9.1Rules of Identification of Organic Compounds by UV Spectrum30

2.9.2Identification of Isomer31

References32

Problems32



Chapter 3 Infrared Spectroscopy34

3.1Introductions of Infrared Spectroscopy34

3.1.1The Representation Method of Infrared Spectrum34

3.1.2Development of IR Spectroscopy35

3.2Basic Principle of Infrared Spectrum37

3.2.1Classical Harmonic Oscillator37

3.2.2Quantum Mechanical Harmonic Oscillator39

3.2.3Degrees of Freedom41

3.2.4Modes of Atomic Vibrations42

3.2.5Certain Terms43

3.2.6Factors Affecting Absorption Intensity44

3.2.7Important Regions in IR Spectra46

3.3Characteristic Group Absorptions of Organic Compounds47

3.3.1Alkanes47

3.3.2Alkenes47

3.3.3Alkynes49

3.3.4Aromatic Hydrocarbons50

3.3.5Alcohols£¬Phenols£¬and Ethers50

3.3.6Carbonyl Groups53

3.3.7Carboxylic Amide57

3.3.8Other Nitrogen Containing Compounds58

3.4Interpretation of IR Spectra59

References60

Problems61



Chapter 4 Mass Spectrometry64

4.1Introduction64

4.1.1Principles64

4.1.2Instrumentation65

4.2Ionization Methods66

4.2.1Electron Ionization67

4.2.2Chemical Ionization68

4.2.3Electrospray Ionization69

4.2.4Atmospheric Pressure Chemical Ionization70

4.2.5Field Desorption Ionization70

4.2.6Fast Atom Bombardment Ionization71

4.2.7Matrix-Assisted Laser Desorption Ionization71

4.3Mass Analysers73

4.3.1Magnetic Sector Mass Spectrometers74

4.3.2Quadrupole Mass Spectrometers75

4.3.3Ion Trap Mass Spectrometers76

4.3.4Time-of-Flight Mass Spectrometers77

4.3.5Tandem Mass Spectrometers77

4.4Base Peak£¬Molecular Ions£¬Fragment Ions and Metastable Ions78

4.4.1Base Peak78

4.4.2Molecular Ions79

4.4.3Fragment Ions79

4.4.4Metastable Ions79

4.5Recognition of the Molecular Ion Peak80

4.6Determination of a Molecular Formula81

4.7Fragmentation 83

4.7.1Representation of Fragmentation Processes83

4.7.2Simple Cleavage83

4.8Rearrangements85

4.9Fragmentation Modes of Various Classes of Organic Compounds86

4.9.1Hydrocarbons86

4.9.2Hydroxy Compounds89

4.9.3Ethers92

4.9.4Ketones93

4.9.5Aldehydes94

4.9.6Carboxylic Acids94

4.9.7Carboxylic Esters95

4.9.8Amines96

4.9.9Amides98

References98

Problems99



Chapter 5 Nuclear Magnetic Resonance Spectroscopy101

5.1Introductions of Nuclear Magnetic Resonance101

5.2Principal of Nuclear Magnetic Resonance103

5.31H NMR Spectroscopy105

5.3.1Acquisition of 1H NMR Spectroscopy105

5.3.2Chemical Shift108

5.3.3Integration (Signal Strength)111

5.3.4Factors Influencing the Chemical Shifts112

5.3.5Coupling Constants (Spin-Spin Interactions)116

5.413C NMR Spectroscopy122

5.4.1Broadband Decoupled 13C Spectrum122

5.4.2DEPT 13C NMR Spectrum126

5.5Two-Dimensional NMR126

5.6Solid State NMR128

5.6.1Introduction of Solid State NMR128

5.6.2Application of Solid-State NMR in Pharmaceutical Polymorphism130

References132

Problems133



Chapter 6 Single Crystal X-ray Crystallography136

6.1Introductions of X-ray Crystallography136

6.2Crystal and Amorphous Solid137

6.2.1Single Crystal, Non-crystal, Twin Crystal and Powder Crystal139

6.2.2Crystal Properties140

6.2.3Symmetry in Crystals140

6.2.4Crystal Growth144

6.3Discovery and Properties of X-ray148

6.3.1Discovery of X-ray148

6.3.2X-ray Properties150

6.4Diffraction of X-ray by Crystals150

6.4.1Laue Experiment150

6.4.2Brag Equation151

6.4.3Principle of Single Crystal X-ray Diffraction153

6.4.4X-ray Diffraction Data Collection154

6.5Calculations of Electronic Density Map156

6.6The Procedures for Crystal Structure Determination158

6.7Applications of Single Crystal X-ray Crystallography in Drug Discovery and Development160

6.8Summary165

References165

Problems165



Chapter 7 Integrated Spectroscopic Analysis169

7.1Introduction169

7.2General Procedures169

7.3Examples170

7.3.1Compound A170

7.3.2Compound B173

7.3.3Compound C176

7.3.4Compound D180

References185

Problems185



Answer to Problems189

Index198