xiv CONTENTS 14.11 Synthesis of Polysubstituted Benzenes 668 14.12 Nucleophilic Aromatic Substitution 674 14.13 Special Topic:Stable Carbocations in"Superacid" 679 14.14 Special Topic:Benzyne 680 14.15 Special Topic:Biological Synthesis of Aromatic Rings; Phenylalanine 682 14.16 Summary 685 14.17 Additional Problems 688 15 Analytical Chemistry:Spectroscopy 694 15.1 Preview 695 15.2 Chromatography 697 15.3 Mass Spectrometry(MS)699 15.4 Infrared Spectroscopy(IR)707 15.5 H Nuclear Magnetic Resonance Spectroscopy(NMR)713 15.6 NMR Measurements 717 15.7 13C NMR Spectroscopy 740 15.8 Problem Solving:How to Use Spectroscopy to Determine Structure 742 15.9 Special Topic:Dynamic NMR 746 15.10 Summary 750 15.11 Additional Problems 751 16 Carbonyl Chemistry 1:Addition Reactions 762 16.1 Preview 763 16.2 Structure of the Carbon-Oxygen Double Bond 764 16.3 Nomenclature of Carbonyl Compounds 767 16.4 Physical Properties of Carbonyl Compounds 770 16.5 Spectroscopy of Carbonyl Compounds 770 16.6 Reactions of Carbonyl Compounds:Simple Reversible Additions 773 16.7 Equilibrium in Addition Reactions 777 16.8 Other Addition Reactions:Additions of Cyanide and Bisulfite 781 16.9 Addition Reactions Followed by Water Loss:Acetal Formation 783 16.10 Protecting Groups in Synthesis 788 16.11 Addition Reactions of Nitrogen Bases: Imine and Enamine Formation 790 16.12 Organometallic Reagents 797
14.11 Synthesis of Polysubstituted Benzenes 668 14.12 Nucleophilic Aromatic Substitution 674 14.13 Special Topic: Stable Carbocations in “Superacid” 679 14.14 Special Topic: Benzyne 680 14.15 Special Topic: Biological Synthesis of Aromatic Rings; Phenylalanine 682 14.16 Summary 685 14.17 Additional Problems 688 15 Analytical Chemistry: Spectroscopy 694 15.1 Preview 695 15.2 Chromatography 697 15.3 Mass Spectrometry (MS) 699 15.4 Infrared Spectroscopy (IR) 707 15.5 1 H Nuclear Magnetic Resonance Spectroscopy (NMR) 713 15.6 NMR Measurements 717 15.7 13C NMR Spectroscopy 740 15.8 Problem Solving: How to Use Spectroscopy to Determine Structure 742 15.9 Special Topic: Dynamic NMR 746 15.10 Summary 750 15.11 Additional Problems 751 16 Carbonyl Chemistry 1: Addition Reactions 762 16.1 Preview 763 16.2 Structure of the Carbon–Oxygen Double Bond 764 16.3 Nomenclature of Carbonyl Compounds 767 16.4 Physical Properties of Carbonyl Compounds 770 16.5 Spectroscopy of Carbonyl Compounds 770 16.6 Reactions of Carbonyl Compounds: Simple Reversible Additions 773 16.7 Equilibrium in Addition Reactions 777 16.8 Other Addition Reactions: Additions of Cyanide and Bisulfite 781 16.9 Addition Reactions Followed by Water Loss: Acetal Formation 783 16.10 Protecting Groups in Synthesis 788 16.11 Addition Reactions of Nitrogen Bases: Imine and Enamine Formation 790 16.12 Organometallic Reagents 797 xiv CONTENTS
CONTENTS 16.13 Irreversible Addition Reactions:A General Synthesis of Alcohols 799 16.14 Oxidation of Alcohols to Carbonyl Compounds 802 16.15 Retrosynthetic Alcohol Synthesis 807 16.16 Oxidation of Thiols and Other Sulfur Compounds 809 16.17 The Wittig Reaction 811 16.18 Special Topic:Biological Oxidation 813 16.19 Summary 816 16.20 Additional Problems 821 17 Carboxylic Acids 828 17.1 Preview829 17.2 Nomenclature and Properties of Carboxylic Acids 830 17.3 Structure of Carboxylic Acids 832 17.4 Infrared and Nuclear Magnetic Resonance Spectra of Carboxylic Acids 833 17.5 Acidity and Basicity of Carboxylic Acids 834 17.6 Synthesis of Carboxylic Acids 839 17.7 Reactions of Carboxylic Acids 841 17.8 Special Topic:Fatty Acids 862 17.9 Summary 867 17.10 Additional Problems 870 18 Derivatives of Carboxylic Acids:Acyl Compounds 876 18.1 Preview 877 18.2 Nomenclature 879 18.3 Physical Properties and Structures of Acyl Compounds 884 18.4 Acidity and Basicity of Acyl Compounds 885 18.5 Spectral Characteristics 887 18.6 Reactions of Acid Chlorides:Synthesis of Acyl Compounds 889 18.7 Reactions of Anhydrides 894 18.8 Reactions of Esters 895 18.9 Reactions of Amides 901 18.10 Reactions of Nitriles 904 18.11 Reactions of Ketenes 907 18.12 Special Topic:Other Synthetic Routes to Acid Derivatives 907 18.13 Special Topic:Thermal Elimination Reactions of Esters 912
16.13 Irreversible Addition Reactions: A General Synthesis of Alcohols 799 16.14 Oxidation of Alcohols to Carbonyl Compounds 802 16.15 Retrosynthetic Alcohol Synthesis 807 16.16 Oxidation of Thiols and Other Sulfur Compounds 809 16.17 The Wittig Reaction 811 16.18 Special Topic: Biological Oxidation 813 16.19 Summary 816 16.20 Additional Problems 821 17 Carboxylic Acids 828 17.1 Preview 829 17.2 Nomenclature and Properties of Carboxylic Acids 830 17.3 Structure of Carboxylic Acids 832 17.4 Infrared and Nuclear Magnetic Resonance Spectra of Carboxylic Acids 833 17.5 Acidity and Basicity of Carboxylic Acids 834 17.6 Synthesis of Carboxylic Acids 839 17.7 Reactions of Carboxylic Acids 841 17.8 Special Topic: Fatty Acids 862 17.9 Summary 867 17.10 Additional Problems 870 18 Derivatives of Carboxylic Acids: Acyl Compounds 876 18.1 Preview 877 18.2 Nomenclature 879 18.3 Physical Properties and Structures of Acyl Compounds 884 18.4 Acidity and Basicity of Acyl Compounds 885 18.5 Spectral Characteristics 887 18.6 Reactions of Acid Chlorides: Synthesis of Acyl Compounds 889 18.7 Reactions of Anhydrides 894 18.8 Reactions of Esters 895 18.9 Reactions of Amides 901 18.10 Reactions of Nitriles 904 18.11 Reactions of Ketenes 907 18.12 Special Topic: Other Synthetic Routes to Acid Derivatives 907 18.13 Special Topic: Thermal Elimination Reactions of Esters 912 CONTENTS xv
xvi CONTENTS 18.14 Special Topic:A Family of Concerted Rearrangements of Acyl Compounds 914 18.15 Summary 921 18.16 Additional Problems 925 19 Carbonyl Chemistry 2:Reactions at the o Position 931 19.1 Preview 932 19.2 Many Carbonyl Compounds Are Weak Bronsted Acids 933 19.3 Racemization of Enols and Enolates 944 19.4 Halogenation in the a Position 946 19.5 Alkylation in the a Position 954 19.6 Addition of Carbonyl Compounds to the a Position: The Aldol Condensation 965 19.7 Reactions Related to the Aldol Condensation 980 19.8 Addition of Acid Derivatives to the a.Position: The Claisen Condensation 985 19.9 Variations on the Claisen Condensation 992 19.10 Special Topic:Forward and Reverse Claisen Condensations in Biology 996 19.11 Condensation Reactions in Combination 998 19.12 Special Topic:Alkylation of Dithianes 1001 19.13 Special Topic:Amines in Condensation Reactions, the Mannich Reaction 1003 19.14 Special Topic:Carbonyl Compounds without a.Hydrogens 1004 19.15 Special Topic:The Aldol Condensation in the Real World,an Introduction to Modern Synthesis 1007 19.16 Summary 1010 19.17 Additional Problems 1017 20 Special Topic:Reactions Controlled by Orbital Symmetry 1030 20.1 Preview 1031 20.2 Concerted Reactions 1032 20.3 Electrocyclic Reactions 1034 20.4 Cycloaddition Reactions 1043 20.5 Sigmatropic Shift Reactions 1048 20.6 The Cope Rearrangement 1059 20.7 A Molecule with a Fluxional Structure 1063 20.8 How to Work Orbital Symmetry Problems 1071
18.14 Special Topic: A Family of Concerted Rearrangements of Acyl Compounds 914 18.15 Summary 921 18.16 Additional Problems 925 19 Carbonyl Chemistry 2: Reactions at the Position 931 19.1 Preview 932 19.2 Many Carbonyl Compounds Are Weak Brønsted Acids 933 19.3 Racemization of Enols and Enolates 944 19.4 Halogenation in the α Position 946 19.5 Alkylation in the α Position 954 19.6 Addition of Carbonyl Compounds to the α Position: The Aldol Condensation 965 19.7 Reactions Related to the Aldol Condensation 980 19.8 Addition of Acid Derivatives to the α Position: The Claisen Condensation 985 19.9 Variations on the Claisen Condensation 992 19.10 Special Topic: Forward and Reverse Claisen Condensations in Biology 996 19.11 Condensation Reactions in Combination 998 19.12 Special Topic: Alkylation of Dithianes 1001 19.13 Special Topic: Amines in Condensation Reactions, the Mannich Reaction 1003 19.14 Special Topic: Carbonyl Compounds without α Hydrogens 1004 19.15 Special Topic: The Aldol Condensation in the Real World, an Introduction to Modern Synthesis 1007 19.16 Summary 1010 19.17 Additional Problems 1017 20 Special Topic: Reactions Controlled by Orbital Symmetry 1030 20.1 Preview 1031 20.2 Concerted Reactions 1032 20.3 Electrocyclic Reactions 1034 20.4 Cycloaddition Reactions 1043 20.5 Sigmatropic Shift Reactions 1048 20.6 The Cope Rearrangement 1059 20.7 A Molecule with a Fluxional Structure 1063 20.8 How to Work Orbital Symmetry Problems 1071 xvi CONTENTS
CONTENTS xvii 20.9 Summary 1073 20.10 Additional Problems 1074 21 Special Topic:Intramolecular Reactions and Neighboring Group Participation 1080 21.1 Preview 1081 21.2 Heteroatoms as Neighboring Groups 1083 21.3 Neighboring Systems 1096 21.4 Single Bonds as Neighboring Groups 1108 21.5 Coates'Cation 1117 21.6 Summary 1118 21.7 Additional Problems 1118 22 Special Topic:Carbohydrates 1124 22.1 Preview 1125 22.2 Nomenclature and Structure of Carbohydrates 1126 22.3 Formation of Carbohydrates 1138 22.4 Reactions of Carbohydrates 1140 22.5 The Fischer Determination of the Structure of D-Glucose (and the 15 Other Aldohexoses)1153 22.6 Special Topic:An Introduction to Di-and Polysaccharides 1161 22.7 Summary 1168 22.8 Additional Problems 1170 23 Special Topic:Amino Acids and Polyamino Acids (Peptides and Proteins)1173 23.1 Preview 1174 23.2 Amino Acids 1175 23.3 Reactions of Amino Acids 1186 23.4 Peptide Chemistry 1189 23.5 Nucleosides,Nucleotides,and Nucleic Acids 1210 23.6 Summary 1215 23.7 Additional Problems 1218 Glossary G-1 Credits C-1 Index I-1
20.9 Summary 1073 20.10 Additional Problems 1074 21 Special Topic: Intramolecular Reactions and Neighboring Group Participation 1080 21.1 Preview 1081 21.2 Heteroatoms as Neighboring Groups 1083 21.3 Neighboring π Systems 1096 21.4 Single Bonds as Neighboring Groups 1108 21.5 Coates’ Cation 1117 21.6 Summary 1118 21.7 Additional Problems 1118 22 Special Topic: Carbohydrates 1124 22.1 Preview 1125 22.2 Nomenclature and Structure of Carbohydrates 1126 22.3 Formation of Carbohydrates 1138 22.4 Reactions of Carbohydrates 1140 22.5 The Fischer Determination of the Structure of D-Glucose (and the 15 Other Aldohexoses) 1153 22.6 Special Topic: An Introduction to Di- and Polysaccharides 1161 22.7 Summary 1168 22.8 Additional Problems 1170 23 Special Topic: Amino Acids and Polyamino Acids (Peptides and Proteins) 1173 23.1 Preview 1174 23.2 Amino Acids 1175 23.3 Reactions of Amino Acids 1186 23.4 Peptide Chemistry 1189 23.5 Nucleosides, Nucleotides, and Nucleic Acids 1210 23.6 Summary 1215 23.7 Additional Problems 1218 Glossary G-1 Credits C-1 Index I-1 CONTENTS xvii
