Organic Chemistry

ISBN-13: 9781119820833 / Angielski / Miękka / 2022 / 1360 str.

David R. Klein

Spis treści

1 A Review of General Chemistry: Electrons, Bonds, and Molecular Properties 11.1 Introduction to Organic Chemistry 21.2 The Structural Theory of Matter 31.3 Electrons, Bonds, and Lewis Structures 41.4 Identifying Formal Charges 71.5 Induction and Polar Covalent Bonds 81.6 Reading Bond- Line Structures 111.7 Atomic Orbitals 141.8 Valence Bond Theory 171.9 Molecular Orbital Theory 181.10 Hybridized Atomic Orbitals 201.11 Predicting Molecular Geometry: VSEPR Theory 261.12 Dipole Moments and Molecular Polarity 301.13 Intermolecular Forces and Physical Properties 33WorldLinks Biomimicry and Gecko Feet 37BioLinks Drug- Receptor Interactions 381.14 Solubility 39BioLinks Propofol: The Importance of Drug Solubility 40Review of Concepts and Vocabulary * SkillBuilder Review Practice Problems * Integrated Problems * Challenge Problems2 Molecular Representations 492.1 Molecular Representations 502.2 Bond- Line Structures 522.3 Identifying Functional Groups 54BioLinks Marine Natural Products 552.4 Carbon Atoms with Formal Charges 572.5 Identifying Lone Pairs 572.6 Three- Dimensional Bond- Line Structures 60BioLinks The Opioids 612.7 Introduction to Resonance 622.8 Curved Arrows 642.9 Formal Charges in Resonance Structures 662.10 Drawing Resonance Structures via Pattern Recognition 682.11 Assessing the Relative Importance of Resonance Structures 732.12 The Resonance Hybrid 772.13 Delocalized and Localized Lone Pairs 79Review of Concepts and Vocabulary * SkillBuilder Review Practice Problems * Integrated Problems * Challenge Problems3 Acids and Bases 913.1 Introduction to Brønsted- Lowry Acids and Bases 923.2 Flow of Electron Density: Curved- Arrow Notation 92BioLinks Antacids and Heartburn 943.3 Brønsted- Lowry Acidity: Quantitative Perspective 95BioLinks Drug Distribution and pK a 1013.4 Brønsted- Lowry Acidity: Qualitative Perspective 1023.5 Brønsted- Lowry Acidity: Assessing the Relative Acidity of Cationic Acids 1133.6 Position of Equilibrium and Choice of Reagents 1183.7 Leveling Effect 1213.8 Solvating Effects 1223.9 Counterions 123WorldLinks Baking Soda versus Baking Powder 1233.10 Lewis Acids and Bases 124Review of Concepts and Vocabulary * SkillBuilder Review Practice Problems * Integrated Problems * Challenge Problems4 Alkanes and Cycloalkanes 1374.1 Introduction to Alkanes 1384.2 Nomenclature of Alkanes 138WorldLinks Pheromones: Chemical Messengers 142BioLinks Naming Drugs 1504.3 Constitutional Isomers of Alkanes 1514.4 Relative Stability of Isomeric Alkanes 1524.5 Sources and Uses of Alkanes 153WorldLinks An Introduction to Polymers 1554.6 Drawing Newman Projections 1554.7 Conformational Analysis of Ethane and Propane 1574.8 Conformational Analysis of Butane 159BioLinks Drugs and Their Conformations 1634.9 Cycloalkanes 163BioLinks Cyclopropane as an Inhalation Anesthetic 1654.10 Conformations of Cyclohexane 1664.11 Drawing Chair Conformations 1674.12 Monosubstituted Cyclohexane 1694.13 Disubstituted Cyclohexane 1714.14 cis-trans Stereoisomerism 1754.15 Polycyclic Systems 176Review of Concepts and Vocabulary * SkillBuilder Review Practice Problems * Integrated Problems * Challenge Problems5 Stereoisomerism 1875.1 Overview of Isomerism 1885.2 Introduction to Stereoisomerism 189WorldLinks The Sense of Smell 1945.3 Designating Configuration Using the Cahn-Ingold-Prelog System 194BioLinks Chiral Drugs 1995.4 Optical Activity 2005.5 Stereoisomeric Relationships: Enantiomers and Diastereomers 2065.6 Symmetry and Chirality 2095.7 Fischer Projections 2135.8 Conformationally Mobile Systems 2155.9 Chirality without a Chiral Center 2165.10 Resolution of Racemic Mixtures 2175.11 Asymmetric Synthesis: Stereoselective and Stereospecific Reactions 219Review of Concepts and Vocabulary * SkillBuilder Review Practice Problems * Integrated Problems * Challenge Problems6 Chemical Reactivity and Mechanisms 2296.1 Enthalpy 2306.2 Entropy 2336.3 Gibbs Free Energy 235WorldLinks Explosives 236WorldLinks Do Living Organisms Violate the Second Law of Thermodynamics? 2386.4 Equilibria 2386.5 Kinetics 240BioLinks Nitroglycerin: An Explosive with Medicinal Properties 243WorldLinks Beer Making 2446.6 Energy Diagrams 2456.7 Nucleophiles and Electrophiles 2486.8 Mechanisms and Arrow Pushing 2526.9 Combining the Patterns of Arrow Pushing 2576.10 Drawing Curved Arrows 2596.11 Carbocation Rearrangements 2626.12 Reversible and Irreversible Reaction Arrows 264Review of Concepts and Vocabulary * SkillBuilder Review Practice Problems * Integrated Problems * Challenge Problems7 Substitution Reactions 2777.1 Introduction to Substitution Reactions 2787.2 Alkyl Halides 2797.3 Possible Mechanisms for Substitution Reactions 2837.4 The S N 2 Mechanism 285BioLinks Pharmacology and Drug Design 2917.5 Nucleophilic Strength in S N 2 Reactions 293BioLinks S N 2 Reactions in Biological Systems--Methylation 2937.6 The S N 1 Mechanism 2957.7 Solvent Effects in Substitution Reactions 301Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems * Integrated Problems Challenge Problems8 Alkenes: Structure and Preparation via Elimination Reactions 3138.1 Introduction to Elimination Reactions 3148.2 Stereoisomerism in Alkenes 314BioLinks Phototherapy Treatment for Neonatal Jaundice 3178.3 Stability of Alkenes and Cycloalkenes 3198.4 Possible Mechanisms for Elimination Reactions 3218.5 The E2 Mechanism 3238.6 Regiochemical and Stereochemical Outcomes for E2 Reactions 3258.7 The E1 Mechanism 3358.8 Predicting Products: Substitution vs. Elimination 3428.9 Substitution and Elimination Reactions with Other Substrates 3488.10 Synthesis Strategies - Substitution and Elimination 352BioLinks Radiolabeled Compounds in Diagnostic Medicine 356SpecialTopic Kinetic Isotope Effects 361Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems9 Addition Reactions of Alkenes 3719.1 Introduction to Addition Reactions 3729.2 Alkenes in Nature and in Industry 373WorldLinks Pheromones to Control Insect Populations 3739.3 Nomenclature of Alkenes 3749.4 Addition vs. Elimination: A Thermodynamic Perspective 3769.5 Hydrohalogenation 377WorldLinks Cationic Polymerization and Polystyrene 3849.6 Acid-Catalyzed Hydration 3859.7 Oxymercuration-Demercuration 3899.8 Hydroboration-Oxidation 3909.9 Catalytic Hydrogenation 396WorldLinks Partially Hydrogenated Fats and Oils 4019.10 Halogenation and Halohydrin Formation 4029.11 Anti Dihydroxylation 4069.12 Syn Dihydroxylation 4099.13 Oxidative Cleavage 4119.14 Predicting the Products of an Addition Reaction 4139.15 Synthesis Strategies 415Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems10 Alkynes 43110.1 Introduction to Alkynes 432BioLinks The Role of Molecular Rigidity 434WorldLinks Conducting Organic Polymers 43510.2 Nomenclature of Alkynes 43510.3 Acidity of Acetylene and Terminal Alkynes 43710.4 Preparation of Alkynes 44010.5 Reduction of Alkynes 44210.6 Hydrohalogenation of Alkynes 44510.7 Hydration of Alkynes 44710.8 Halogenation of Alkynes 45310.9 Ozonolysis of Alkynes 45310.10 Alkylation of Terminal Alkynes 45410.11 Synthesis Strategies 456Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems11 Radical Reactions 46711.1 Radicals 46811.2 Common Patterns in Radical Mechanisms 47311.3 Chlorination of Methane 47611.4 Thermodynamic Considerations for Halogenation Reactions 48011.5 Selectivity of Halogenation 48211.6 Stereochemistry of Halogenation 48511.7 Allylic Bromination 48711.8 Atmospheric Chemistry and the Ozone Layer 490WorldLinks Fighting Fires with Chemicals 49211.9 Autooxidation and Antioxidants 493BioLinks Why Is an Overdose of Acetaminophen Fatal? 49511.10 Radical Addition of HBr: Anti-Markovnikov Addition 49611.11 Radical Polymerization 50011.12 Radical Processes in the Petrochemical Industry 50211.13 Halogenation as a Synthetic Technique 502Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems12 Systematic Approach to Synthesis 51112.1 One-Step Syntheses 51212.2 Functional Group Transformations 51312.3 Reactions That Change the Carbon Skeleton 517BioLinks Vitamins 51912.4 How to Approach a Synthesis Problem 520BioLinks The Total Synthesis of Vitamin B 12 52412.5 Multi- Step Synthesis and Retrosynthetic Analysis 526WorldLinks Retrosynthetic Analysis 53112.6 Green Chemistry 53112.7 Practical Tips for Increasing Proficiency 532BioLinks Total Synthesis of Taxol 533Review of Concepts and Vocabulary * SkillBuilder Review Practice Problems * Integrated Problems * Challenge Problems Review of Reactions * 13 Alcohols and Phenols 54113.1 Structure and Properties of Alcohols 542BioLinks Chain Length as a Factor in Drug Design 54613.2 Acidity of Alcohols and Phenols 54713.3 Preparation of Alcohols via Substitution or Addition 55013.4 Preparation of Alcohols via Reduction 55113.5 Preparation of Diols 558WorldLinks Antifreeze 55913.6 Preparation of Alcohols via Grignard Reagents 55913.7 Protection of Alcohols 56413.8 Preparation of Phenols 56513.9 Reactions of Alcohols: Substitution and Elimination 566BioLinks Drug Metabolism 56913.10 Reactions of Alcohols: Oxidation 57113.11 Biological Redox Reactions 575BioLinks Biological Oxidation of Methanol and Ethanol 57713.12 Oxidation of Phenol 57713.13 Synthesis Strategies 579Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems14 Ethers and Epoxides; Thiols and Sulfides 59714.1 Introduction to Ethers 59814.2 Nomenclature of Ethers 59814.3 Structure and Properties of Ethers 600BioLinks Ethers as Inhalation Anesthetics 60114.4 Crown Ethers 602WorldLinks Chelating Agents in the Food Industry and in Medicine 60414.5 Preparation of Ethers 60514.6 Reactions of Ethers 60814.7 Nomenclature of Epoxides 611BioLinks Epothilones as Novel Anticancer Agents 61214.8 Preparation of Epoxides 612BioLinks Active Metabolites and Drug Interactions 61514.9 Enantioselective Epoxidation 61514.10 Ring- Opening Reactions of Epoxides 617WorldLinks Ethylene Oxide as a Sterilizing Agent for Sensitive Medical Equipment 620BioLinks Cigarette Smoke and Carcinogenic Epoxides 62414.11 Thiols and Sulfides 62514.12 Synthesis Strategies Involving Epoxides 629Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems15 Infrared Spectroscopy and Mass Spectrometry 64715.1 Introduction to Spectroscopy 648WorldLinks Microwave Ovens 65015.2 IR Spectroscopy 650BioLinks IR Thermal Imaging for Cancer Detection 65115.3 Signal Characteristics: Wavenumber 65215.4 Signal Characteristics: Intensity 657WorldLinks IR Spectroscopy for Testing Blood Alcohol Levels 65915.5 Signal Characteristics: Shape 65915.6 Analyzing an IR Spectrum 66315.7 Using IR Spectroscopy to Distinguish between Two Compounds 66815.8 Introduction to Mass Spectrometry 669WorldLinks Mass Spectrometry for Detecting Explosives 67115.9 Analyzing the (M) +* Peak 67215.10 Analyzing the (M+1) +* Peak 67315.11 Analyzing the (M+2) +* Peak 67515.12 Analyzing the Fragments 67715.13 High- Resolution Mass Spectrometry 68015.14 Gas Chromatography- Mass Spectrometry 68215.15 Liquid Chromatography-Mass Spectrometry 68215.16 Mass Spectrometry of Large Biomolecules 683WorldLinks Medical Applications of Mass Spectrometry 68315.17 Hydrogen Deficiency Index: Degrees of Unsaturation 684Review of Concepts and Vocabulary * SkillBuilder Review Practice Problems * Integrated Problems * Challenge Problems16 Nuclear Magnetic Resonance Spectroscopy 69516.1 Introduction to NMR Spectroscopy 69616.2 Acquiring a 1 H NMR Spectrum 69816.3 Characteristics of a 1 H NMR Spectrum 69916.4 Number of Signals 70016.5 Chemical Shift 70616.6 Integration 71316.7 Multiplicity 71616.8 Drawing the Expected 1 H NMR Spectrum of a Compound 72416.9 Using 1 H NMR Spectroscopy to Distinguish between Compounds 726BioLinks Detection of Impurities in Heparin Sodium Using 1 H NMR Spectroscopy 72816.10 Analyzing a 1 H NMR Spectrum 72916.11 Acquiring a 13 C NMR Spectrum 73216.12 Chemical Shifts in 13 C NMR Spectroscopy 73216.13 DEPT 13 C NMR Spectroscopy 735BioLinks Magnetic Resonance Imaging (MRI) 738Review of Concepts and Vocabulary * SkillBuilder Review Practice Problems * Integrated Problems * Challenge Problems17 Conjugated Pi Systems and Pericyclic Reactions 74917.1 Classes of Dienes 75017.2 Conjugated Dienes 75117.3 Molecular Orbital Theory 75317.4 Electrophilic Addition 75717.5 Thermodynamic Control vs. Kinetic Control 760WorldLinks Natural and Synthetic Rubbers 76317.6 An Introduction to Pericyclic Reactions 76417.7 Diels-Alder Reactions 76517.8 MO Description of Cycloadditions 77117.9 Electrocyclic Reactions 77417.10 Sigmatropic Rearrangements 779BioLinks The Photoinduced Biosynthesis of Vitamin D 78117.11 Other Pericyclic Reactions 78217.12 UV-Vis Spectroscopy 784WorldLinks Sunscreens 78817.13 Photoreductions and Photorearrangements 78817.14 Color 792WorldLinks Bleach 79217.15 Chemistry of Vision 793Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems18 Aromatic Compounds 80318.1 Introduction to Aromatic Compounds 804WorldLinks What Is Coal? 80518.2 Nomenclature of Benzene Derivatives 80518.3 Structure of Benzene 80818.4 Stability of Benzene 809WorldLinks Molecular Cages 81318.5 Aromatic Compounds Other Than Benzene 816BioLinks The Development of Nonsedating Antihistamines 82118.6 Reactions at the Benzylic Position 82318.7 Reduction of Benzene and Its Derivatives 82818.8 Spectroscopy of Aromatic Compounds 830WorldLinks Buckyballs and Nanotubes 833Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems19 Aromatic Substitution Reactions 84319.1 Introduction to Electrophilic Aromatic Substitution 84419.2 Halogenation 844BioLinks Halogenation in Drug Design 84719.3 Sulfonation 848WorldLinks What Are Those Colors in Fruity Pebbles? 84919.4 Nitration 850BioLinks The Discovery of Prodrugs 85119.5 Friedel-Crafts Alkylation 85219.6 Friedel-Crafts Acylation 85519.7 Activating Groups 85619.8 Deactivating Groups 86019.9 Halogens: The Exception 86219.10 Determining the Directing Effects of a Substituent 86319.11 Multiple Substituents 86719.12 Synthesis Strategies 87219.13 Nucleophilic Aromatic Substitution 87819.14 Elimination-Addition 88019.15 Identifying the Mechanism of an Aromatic Substitution Reaction 882Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems20 Aldehydes and Ketones 89520.1 Introduction to Aldehydes and Ketones 89620.2 Nomenclature 89720.3 Preparation of Aldehydes and Ketones: A Review 89920.4 Introduction to Nucleophilic Addition Reactions 90020.5 Oxygen Nucleophiles 903BioLinks Acetals as Prodrugs 90920.6 Nitrogen Nucleophiles 911WorldLinks Beta- Carotene and Vision 91520.7 Hydrolysis of Acetals, Imines, and Enamines 919BioLinks Prodrugs 92220.8 Sulfur Nucleophiles 92220.9 Hydrogen Nucleophiles 92320.10 Carbon Nucleophiles 924WorldLinks Organic Cyanide Compounds in Nature 92720.11 Baeyer- Villiger Oxidation of Aldehydes and Ketones 93320.12 Synthesis Strategies 93520.13 Spectroscopic Analysis of Aldehydes and Ketones 938Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems21 Carboxylic Acids and Their Derivatives 95121.1 Introduction to Carboxylic Acids 95221.2 Nomenclature of Carboxylic Acids 95221.3 Structure and Properties of Carboxylic Acids 95421.4 Preparation of Carboxylic Acids 95721.5 Reactions of Carboxylic Acids 95821.6 Introduction to Carboxylic Acid Derivatives 959BioLinks Sedatives 96121.7 Reactivity of Carboxylic Acid Derivatives 96321.8 Preparation and Reactions of Acid Chlorides 97021.9 Preparation and Reactions of Acid Anhydrides 975BioLinks How Does Aspirin Work? 97721.10 Preparation of Esters 97821.11 Reactions of Esters 979WorldLinks How Soap Is Made 980BioLinks Esters as Prodrugs 98121.12 Preparation and Reactions of Amides 984WorldLinks Polyesters and Polyamides 985BioLinks Beta-Lactam Antibiotics 98821.13 Preparation and Reactions of Nitriles 98921.14 Synthesis Strategies 99221.15 Spectroscopy of Carboxylic Acids and Their Derivatives 997Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems22 Alpha Carbon Chemistry: Enols and Enolates 100922.1 Introduction to Alpha Carbon Chemistry: Enols and Enolates 101022.2 Alpha Halogenation of Enols and Enolates 101722.3 Aldol Reactions 1022WorldLinks Muscle Power 102522.4 Claisen Condensations 103322.5 Alkylation of the Alpha Position 103522.6 Conjugate Addition Reactions 1044BioLinks Glutathione Conjugation and Biochemical Michael Reactions 104622.7 Synthesis Strategies 1050Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems23 Amines 106723.1 Introduction to Amines 1068BioLinks Drug Metabolism Studies 106923.2 Nomenclature of Amines 106923.3 Properties of Amines 1072BioLinks Fortunate Side Effects 1073WorldLinks Chemical Warfare Among Ants 107723.4 Preparation of Amines: A Review 107823.5 Preparation of Amines via Substitution Reactions 107923.6 Preparation of Amines via Reductive Amination 108223.7 Synthesis Strategies 108423.8 Acylation of Amines 108723.9 Hofmann Elimination 108823.10 Reactions of Amines with Nitrous Acid 109123.11 Reactions of Aryl Diazonium Ions 109323.12 Nitrogen Heterocycles 1097BioLinks H 2 -Receptor Antagonists and the Development of Cimetidine 109823.13 Spectroscopy of Amines 1100Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems24 Introduction to Organometallic Compounds 111324.1 General Properties of Organometallic Compounds 111424.2 Organolithium and Organomagnesium Compounds 111524.3 Lithium Dialkyl Cuprates (Gilman Reagents) 111824.4 The Simmons-Smith Reaction and Carbenoids 112224.5 Stille Coupling 112524.6 Suzuki Coupling 113124.7 Negishi Coupling 113624.8 The Heck Reaction 114124.9 Sonogashira Coupling 114624.10 Hiyama Coupling 115124.11 Alkene Metathesis 1154WorldLinks Improving Biodiesel via Alkene Metathesis 1159Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems25 Carbohydrates 117525.1 Introduction to Carbohydrates 117625.2 Classification of Monosaccharides 117625.3 Configuration of Aldoses 117925.4 Configuration of Ketoses 118025.5 Cyclic Structures of Monosaccharides 118225.6 Reactions of Monosaccharides 118925.7 Disaccharides 1196BioLinks Lactose Intolerance 1199WorldLinks Artificial Sweeteners 120025.8 Polysaccharides 120125.9 Amino Sugars 120225.10 N-Glycosides 1203BioLinks Aminoglycoside Antibiotics 1204BioLinks Erythromycin Biosynthesis 1208Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems26 Amino Acids, Peptides, and Proteins 121726.1 Introduction to Amino Acids, Peptides, and Proteins 121826.2 Structure and Properties of Amino Acids 1219WorldLinks Nutrition and Sources of Amino Acids 1221WorldLinks Forensic Chemistry and Fingerprint Detection 122526.3 Amino Acid Synthesis 122626.4 Structure of Peptides 1230BioLinks Polypeptide Antibiotics 123526.5 Sequencing a Peptide 123626.6 Peptide Synthesis 123926.7 Protein Structure 1247BioLinks Diseases Caused by Misfolded Proteins 125026.8 Protein Function 1250Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems27 Lipids 126127.1 Introduction to Lipids 126227.2 Waxes 126327.3 Triglycerides 126327.4 Reactions of Triglycerides 1267WorldLinks Soaps Versus Synthetic Detergents 127127.5 Phospholipids 1275BioLinks Polyether Antibiotics 127827.6 Steroids 1279BioLinks Cholesterol and Heart Disease 1282BioLinks Anabolic Steroids and Competitive Sports 128427.7 Prostaglandins 1285BioLinks NSAIDs and COX-2 Inhibitors 128627.8 Terpenes 1287Review of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge Problems28 Synthetic Polymers* 28.1 Introduction to Synthetic Polymers28.2 Nomenclature of Synthetic Polymers28.3 Copolymers28.4 Polymer Classification by Reaction Type28.5 Polymer Classification by Mode of Assembly28.6 Polymer Classification by Structure28.7 Polymer Classification by PropertiesWorldLinks Safety Glass and Car Windshields28.8 Polymer RecyclingReview of Reactions * Review of Concepts and Vocabulary SkillBuilder Review * Practice Problems Integrated Problems * Challenge ProblemsAppendix A: Nomenclature of Polyfunctional Compounds A1Appendix B: Multiple Choice Questions A5Glossary G1Index I1Selected Answers*