Understanding Organic Chemistry - Ann M. Fabirkiewicz

. .

Résumé :

Preface to the Fourth Edition xi

Preface to the Third Edition xiii

Preface to the Second Edition xv

Preface to the First Edition xvii

About the Companion Website xix

1 Reading Nomenclature 1

1.1 Acyclic Polyfunctional Molecules 2

1.2 Monocyclic Aliphatic Compounds 3

1.3 Bridged Polycyclic Structures 4

1.4 Fused Polycyclic Compounds 6

1.5 Spiro Compounds 10

1.6 Monocyclic Heterocyclic Compounds 11

1.7 Fused-Ring Heterocyclic Compounds 16

1.8 Bridged and Spiro Heterocyclic Compounds 19

Resources 20

Problems 21

References 22

2 Accessing Chemical Information 25

2.1 Databases 25

2.2 Chemical Literature 26

2.3 Synthetic Procedures 28

2.4 Health and Safety Information 29

Problems 32

References 34

3 Stereochemistry 37

3.1 Representations 37

3.2 Vocabulary 39

3.3 Property Differences Among Stereoisomers 42

3.4 Resolution of Enantiomers 46

3.5 Enantioselective Synthesis 49

3.5.1 Chiral Templates 50

3.5.2 Chiral Catalysts 50

3.5.3 Chiral Reagents 51

3.5.4 Substrate-Directed Enantioselective Reactions 52

3.6 Reactions at a Stereogenic Atom 53

3.6.1 Racemization 53

3.6.2 Epimerization 53

3.6.3 Inversion 54

3.6.4 Retention 55

3.6.5 Transfer 56

3.7 Relative and Absolute Configurations 57

3.8 Topism 59

Resources 63

Problems 63

References 70

4 Mechanisms and Predictions 75

4.1 Reaction Coordinate Diagrams and Mechanisms 75

4.2 The Hammond Postulate 77

4.3 Methods for Determining Mechanisms 78

4.3.1 Identification of Products and Intermediates 78

4.3.2 Isotope Tracing 78

4.3.3 Stereochemical Determination 79

4.3.4 Concentration Dependence of Kinetics 81

4.3.5 Isotope Effects in Kinetics 90

4.3.6 Temperature Effects on Kinetics 92

4.3.7 Substituent Effects on Kinetics 94

4.4 Worked Examples 100

4.4.1 Reactions in Basic Solutions 100

4.4.2 Reactions in Acidic Solutions 104

4.4.3 Free Radical Reactions 108

4.4.4 Molecular Rearrangements 111

Resource 113

Problems 114

References 126

5 Electron Delocalization Aromatic Character and Pericyclic Reactions 129

5.1 Molecular Orbitals 130

5.2 Aromatic Character 136

5.3 Pericyclic Reactions 141

5.3.1 Cycloaddition Reactions 143

5.3.2 Electrocyclic Reactions 148

5.3.3 Sigmatropic Reactions 153

5.3.4 Ene Reactions 156

5.3.5 Selection Rules for Pericyclic Reactions 158

Resources 159

Problems 159

References 167

6 Functional Group Transformations 171

6.1 Carboxylic Acids and Related Derivatives 172

6.1.1 Carboxylic Acids 172

6.1.2 Carboxylic Esters 174

6.1.3 Carboxylic Amides 176

6.1.4 Carboxylic Acid Halides 176

6.1.5 Carboxylic Anhydrides 176

6.1.6 Nitriles 177

6.1.7 Ortho Esters 178

6.2 Aldehydes Ketones and Derivatives 179

6.2.1 Aldehydes 179

6.2.2 Ketones 182

6.2.3 Imines and Enamines 182

6.2.4 Acetals 183

6.2.5 Vinyl Ethers 185

6.3 Alcohols 186

6.4 Ethers 187

6.5 Alkyl Halides 189

6.5.1 Alkyl Chlorides and Alkyl Bromides 190

6.5.2 Alkyl Iodides 192

6.5.3 Alkyl Fluorides 192

6.6 Amines 194

6.7 Isocyanates 195

6.8 Alkenes 195

6.9 Reductive Removal of Functionality 198

Resources 199

Problems 199

References 206

7 Carbon-Carbon Bond Formation 213