Contents xi 18.10 Limitations on Electrophilic Substitution Reactions with Substituted Benzenes 665 18.11 Disubstituted Benzenes 666 18.12 Synthesis of Benzene Derivatives 668 18.13 Halogenation of Alkyl Benzenes 669 18.14 Oxidation and Reduction of Substituted Benzenes 671 18.15 Multistep Synthesis 675 9 Carboxylic Acids and the Acidity of the O-H Bond 688 19.1 Structure and Bonding 689 19.2 Nomenclature 690 19.3 Physical Properties 692 19.4 Spectroscopic Properties 693 19.5 Interesting Carboxylic Acids 694 Aspirin,Arachidonic Acid,and Prostaglandins69 ration of Carboxylic Acids 697 Reaction ylic Acid eral Features 699 Carboxylic Acids -Str uctive Effe S0bstutedBe cts in Alipl ng Organic Bre rboxylic Acids nzoic Acids 19.12 Extraction 707 19.13 Sulfonic Acids 709 19.14 Amino Acids 710 Key Concepts 713 Problems 714 20 Introduction to Carbonyl Chemistry: Organometallic Reagents;Oxidation and Reduction 721 Introduction 722 General Reactions of Carbonyl Compounds 723 A Preview of Oxidation and Reduction 726 20.4 Reduction of Aldehydes and Ketones 727 20.5 The Stereochemistry of Carbonyl Reduction 729 20.6 Enantioselective Carbonyl Reductions 731 20.7 Reduction of Carboxylic Acids and Their Derivatives 733 20.8 Oxidation of Aldehy 20.9 des 738 etallic Re s739 actio of o me with Alde ydes and Ketones 742 746 Protecting Groups 20.13 Reaction of Organometallic Reagents with Carboxylic Acid Derivatives 750 20.14 Reaction of Organometallic Reagents with Other Compounds 753 20.15 a,B-Unsaturated Carbonyl Compounds 755 20.16 Summary-The Reactions of Organometallic Reagents 758Contents xiii 18.10 Limitations on Electrophilic Substitution Reactions with Substituted Benzenes 665 18.11 Disubstituted Benzenes 666 18.12 Synthesis of Benzene Derivatives 668 18.13 Halogenation of Alkyl Benzenes 669 18.14 Oxidation and Reduction of Substituted Benzenes 671 18.15 Multistep Synthesis 675 Key Concepts 678 Problems 680 19 Carboxylic Acids and the Acidity of the O–H Bond 688 19.1 Structure and Bonding 689 19.2 Nomenclature 690 19.3 Physical Properties 692 19.4 Spectroscopic Properties 693 19.5 Interesting Carboxylic Acids 694 19.6 Aspirin, Arachidonic Acid, and Prostaglandins 696 19.7 Preparation of Carboxylic Acids 697 19.8 Reactions of Carboxylic Acids—General Features 699 19.9 Carboxylic Acids—Strong Organic Brønsted–Lowry Acids 700 19.10 Inductive Effects in Aliphatic Carboxylic Acids 703 19.11 Substituted Benzoic Acids 705 19.12 Extraction 707 19.13 Sulfonic Acids 709 19.14 Amino Acids 710 Key Concepts 713 Problems 714 20 Introduction to Carbonyl Chemistry; Organometallic Reagents; Oxidation and Reduction 721 20.1 Introduction 722 20.2 General Reactions of Carbonyl Compounds 723 20.3 A Preview of Oxidation and Reduction 726 20.4 Reduction of Aldehydes and Ketones 727 20.5 The Stereochemistry of Carbonyl Reduction 729 20.6 Enantioselective Carbonyl Reductions 731 20.7 Reduction of Carboxylic Acids and Their Derivatives 733 20.8 Oxidation of Aldehydes 738 20.9 Organometallic Reagents 739 20.10 Reaction of Organometallic Reagents with Aldehydes and Ketones 742 20.11 Retrosynthetic Analysis of Grignard Products 746 20.12 Protecting Groups 748 20.13 Reaction of Organometallic Reagents with Carboxylic Acid Derivatives 750 20.14 Reaction of Organometallic Reagents with Other Compounds 753 20.15 α,β-Unsaturated Carbonyl Compounds 755 20.16 Summary—The Reactions of Organometallic Reagents 758 smi75625_fm_00i-xxxiv.indd xiii 11/17/09 11:21:30 AM