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Chapter 1 Carbon Compounds and Chemical Bonds |
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1 | (49) |
| Life Is Organic Chemistry (Molecular graphic: Glycine, an organic molecule found in space) |
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1 | (1) |
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2 | (1) |
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1.2 The Development of Organic Chemistry as a Science |
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3 | (1) |
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1.3 The Structural Theory of Organic Chemistry |
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4 | (3) |
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1.4 Chemical Bonds: The Octet Rule |
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7 | (2) |
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1.5 Writing Lewis Structures |
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9 | (1) |
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1.6 Exceptions to the Octet Rule |
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10 | (2) |
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12 | (2) |
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14 | (4) |
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18 | (1) |
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19 | (2) |
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21 | (3) |
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1.12 The Structure of Methane and Ethane: sp^(3) Hybridization |
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24 | (4) |
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1.13 The Structure of Ethene (Ethylene): sp^(2) Hybridization |
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28 | (5) |
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1.14 The Structure of Ethyne (Acetylene): sp Hybridization |
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33 | (2) |
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1.15 A Summary of Important Concepts that Come from Quantum Mechanics |
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35 | (2) |
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1.16 Molecular Geometry: The Valence Shell Electron-Pair Repulsion (VSEPR) Model |
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37 | (3) |
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1.17 Representation of Structural Formulas |
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40 | (10) |
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Chapter 2 Representative Carbon Compounds: Functional Groups, Intermolecular Forces, and Infrared (IR) Spectroscopy |
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50 | (40) |
| Structure Is Everything (Molecular graphic: Crixivan, a drug used against HIV) |
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50 | (1) |
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2.1 Carbon-Carbon Covalent Bonds |
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51 | (1) |
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2.2 Hydrocarbons: Representative Alkanes, Alkenes, Alkynes, and Aromatic Compounds |
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51 | (4) |
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55 | (1) |
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2.4 Polar and Nonpolar Molecules |
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56 | (3) |
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59 | (1) |
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2.6 Alkyl Halides or Haloalkanes |
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60 | (1) |
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61 | (2) |
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63 | (1) |
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63 | (1) |
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2.10 Aldehydes and Ketones |
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64 | (2) |
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2.11 Carboxylic Acids, Amides, and Esters |
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66 | (1) |
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67 | (1) |
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2.13 Summary of Important Families of Organic Compounds |
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68 | (1) |
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2.14 Physical Properties and Molecular Structure |
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68 | (8) |
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2.15 Summary of Attractive Electric Forces |
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76 | (1) |
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2.16 Infrared Spectroscopy: An Instrumental Method for Detecting Functional Groups |
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76 | (14) |
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Chapter 3 An Introduction to Organic Reactions: Acids and Bases |
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90 | (39) |
| Shuttling the Protons (Molecular graphic: Diamox, a drug that prevents altitude sickness) |
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90 | (1) |
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3.1 Reactions and Their Mechanisms |
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91 | (3) |
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94 | (4) |
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The Chemistry of... HOMOs and LUMOs in Reactions |
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98 | (1) |
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3.3 Heterolysis of Bonds to Carbon: Carbocations and Carbanions |
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98 | (1) |
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3.4 Use of Curved Arrows in Illustrating Reactions |
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99 | (2) |
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3.5 The Strength of Acids and Bases: K(a) and pK(a) |
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101 | (3) |
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3.6 Predicting the Outcome of Acid-Base Reactions |
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104 | (2) |
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3.7 The Relationship between Structure and Acidity |
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106 | (4) |
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110 | (1) |
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3.9 The Relationship between the Equilibrium Constant and the Standard Free-Energy Change, (Delta)G^(Degree) |
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111 | (1) |
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3.10 The Acidity of Carboxylic Acids |
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112 | (4) |
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3.11 The Effect of the Solvent on Acidity |
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116 | (1) |
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3.12 Organic Compounds as Bases |
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117 | (2) |
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3.13 A Mechanism for an Organic Reaction |
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119 | (1) |
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3.14 Acids and Bases in Nonaqueous Solutions |
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120 | (3) |
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The Chemistry of... Carbonic Anhydrase |
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121 | (2) |
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3.15 Acid-Base Reactions and the Synthesis of Deuterium- and Tritium-Labeled Compounds |
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123 | (6) |
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Chapter 4 Alkanes: Nomenclature, Conformational Analysis, and an Introduction to Synthesis |
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129 | (55) |
| To Be Flexible or Inflexible--Molecular Structure Makes the Difference (Molecular graphic: A portion of the structure of diamond, an exceptionally rigid molecule) |
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129 | (1) |
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4.1 Introduction to Alkanes and Cycloalkanes |
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130 | (2) |
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132 | (3) |
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4.3 IUPAC Nomenclature of Alkanes, Alkyl Halides, and Alcohols |
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135 | (7) |
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4.4 Nomenclature of Cycloalkanes |
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142 | (2) |
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4.5 Nomenclature of Alkenes and Cycloalkenes |
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144 | (2) |
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4.6 Nomenclature of Alkynes |
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146 | (1) |
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4.7 Physical Properties of Alkanes and Cycloalkanes |
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147 | (2) |
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4.8 Sigma Bonds and Bond Rotation |
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149 | (2) |
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4.9 Conformational Analysis of Butane |
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151 | (2) |
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4.10 The Relative Stabilities of Cycloalkanes: Ring Strain |
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153 | (2) |
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4.11 The Origin of Ring Strain in Cyclopropane and Cyclobutane: Angle Strain and Torsional Strain |
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155 | (2) |
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4.12 Conformations of Cyclohexane |
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157 | (3) |
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4.13 Substituted Cyclohexanes: Axial and Equatorial Hydrogen Atoms |
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160 | (3) |
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4.14 Disubstituted Cycloalkanes: Cis-Trans Isomerism |
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163 | (5) |
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4.15 Bicyclic and Polycyclic Alkanes |
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168 | (1) |
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4.16 Pheromones: Communication by Means of Chemicals |
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169 | (1) |
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4.17 Chemical Reactions of Alkanes |
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170 | (1) |
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4.18 Synthesis of Alkanes and Cycloalkanes |
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170 | (3) |
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4.19 Some General Principles of Structure and Reactivity: A Look Toward Synthesis |
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173 | (1) |
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4.20 An Introduction to Organic Synthesis |
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174 | (10) |
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The Chemistry of... From the Inorganic to the Organic |
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178 | (6) |
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Chapter 5 Stereochemistry: Chiral Molecules |
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184 | (45) |
| The Handedness of Life (Molecular graphic: The mirror-image stereoisomers of alanine, a chiral amino acid) |
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184 | (1) |
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5.1 Isomerism: Constitutional Isomers and Stereoisomers |
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185 | (2) |
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5.2 Enantiomers and Chiral Molecules |
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187 | (4) |
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5.3 The Biological Importance of Chirality |
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191 | (2) |
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5.4 The Historical Origin of Stereochemistry |
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193 | (1) |
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5.5 Tests for Chirality: Planes of Symmetry |
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194 | (1) |
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5.6 Nomenclature of Enantiomers: The (R-S) System |
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195 | (5) |
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5.7 Properties of Enantiomers: Optical Activity |
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200 | (5) |
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5.8 The Origin of Optical Activity |
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205 | (3) |
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5.9 The Synthesis of Chiral Molecules |
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208 | (2) |
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210 | (1) |
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The Chemistry of... Unnatural Protein Enantiomers |
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211 | (1) |
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5.11 Molecules with More Than One Stereocenter |
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211 | (4) |
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5.12 Fischer Projection Formulas |
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215 | (2) |
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5.13 Stereoisomerism of Cyclic Compounds |
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217 | (2) |
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5.14 Relating Configurations through Reactions in Which No Bonds to the Stereocenter Are Broken |
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219 | (4) |
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5.15 Separation of Enantiomers: Resolution |
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223 | (1) |
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5.16 Compounds with Stereocenters Other than Carbon |
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224 | (1) |
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5.17 Chiral Molecules that Do Not Possess a Tetrahedral Atom with Four Different Groups |
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224 | (5) |
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Chapter 6 Ionic Reactions--Nucleophilic Substitution and Elimination Reactions of Alkyl Halides |
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229 | (52) |
| Breaking Bacterial Cell Walls with Organic Chemistry (Molecular graphic: The S(N)2 transition state resulting from collision of a hydroxide anion with chloromethane) |
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229 | (1) |
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230 | (1) |
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6.2 Physical Properties of Organic Halides |
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231 | (1) |
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6.3 Nucleophilic Substitution Reactions |
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231 | (1) |
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232 | (1) |
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233 | (1) |
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6.6 Kinetics of a Nucleophilic Substitution Reaction: An S(N)2 Reaction |
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234 | (1) |
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6.7 A Mechanism for the S(N)2 Reaction |
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235 | (2) |
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6.8 Transition State Theory: Free-Energy Diagrams |
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237 | (3) |
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6.9 The Stereochemistry of S(N)2 Reactions |
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240 | (3) |
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6.10 The Reaction of tert-Butyl Chloride with Hydroxide Ion: An S(N)1 Reaction |
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243 | (1) |
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6.11 A Mechanism for the S(N)1 Reaction |
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244 | (2) |
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246 | (3) |
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6.13 The Stereochemistry of S(N)1 Reactions |
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249 | (2) |
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6.14 Factors Affecting the Rates of S(N)1 and S(N)2 Reactions |
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251 | (10) |
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6.15 Organic Synthesis: Functional Group Transformations Using S(N)2 Reactions |
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261 | (4) |
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The Chemistry of... Biological Methylation: A Biological Nucleophilic Substitution Reaction |
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262 | (3) |
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6.16 Elimination Reactions of Alkyl Halides |
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265 | (2) |
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267 | (1) |
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268 | (1) |
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6.19 Substitution versus Elimination |
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269 | (3) |
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272 | (9) |
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Chapter 7 Alkenes and Alkynes I: Properties and Synthesis. Elimination Reactions of Alkyl Halides |
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281 | (40) |
| Cell Membrane Fluidity (Molecular graphic: cis-9-Octadecenoic acid, an unsaturated fatty acid incorporated into cell membrane phospholipids) |
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281 | (1) |
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282 | (1) |
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7.2 The (E)-(Z) System for Designating Alkene Diastereomers |
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282 | (2) |
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7.3 Relative Stabilities of Alkenes |
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284 | (3) |
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287 | (1) |
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7.5 Synthesis of Alkenes via Elimination Reactions |
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288 | (1) |
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7.6 Dehydrohalogenation of Alkyl Halides |
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288 | (5) |
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7.7 Dehydration of Alcohols |
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293 | (6) |
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7.8 Carbocation Stability and the Occurrence of Molecular Rearrangements |
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299 | (4) |
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7.9 Alkenes by Debromination of Vicinal Dibromides |
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303 | (1) |
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7.10 Synthesis of Alkynes by Elimination Reactions |
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304 | (1) |
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7.11 The Acidity of Terminal Alkynes |
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305 | (1) |
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7.12 Replacement of the Acetylenic Hydrogen Atom of Terminal Alkynes |
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306 | (1) |
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7.13 Hydrogenation of Alkenes |
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307 | (2) |
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The Chemistry of... Hydrogenation in the Food Industry |
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308 | (1) |
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7.14 Hydrogenation: The Function of the Catalyst |
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309 | (1) |
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7.15 Hydrogenation of Alkynes |
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310 | (2) |
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7.16 Molecular Formulas of Hydrocarbons: The Index of Hydrogen Deficiency |
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312 | (9) |
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Chapter 8 Alkenes and Alkynes II: Addition Reactions |
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321 | (45) |
| The Sea: A Treasury of Biologically Active Compounds (Molecular graphic: Dactylyne, a halogenated marine natural product) |
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321 | (1) |
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8.1 Introduction: Additions to Alkenes |
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322 | (2) |
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8.2 Addition of Hydrogen Halides to Alkenes: Markovnikov's Rule |
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324 | (6) |
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8.3 Stereochemistry of the Ionic Addition to an Alkene |
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330 | (1) |
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8.4 Addition of Sulfuric Acid to Alkenes |
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330 | (1) |
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8.5 Addition of Water to Alkenes: Acid-Catalyzed Hydration |
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331 | (3) |
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8.6 Addition of Bromine and Chlorine to Alkenes |
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334 | (1) |
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8.7 Stereochemistry of the Addition of Halogens to Alkenes |
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335 | (4) |
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339 | (3) |
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The Chemistry of... Regioselectivity in Unsymmetrically Substituted Bromonium Ions: Bromonium Ions of Ethene, Propene, and 2-Methylpropene |
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340 | (2) |
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8.9 Divalent Carbon Compounds: Carbenes |
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342 | (2) |
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8.10 Oxidations of Alkenes: Syn Hydroxylation |
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344 | (2) |
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8.11 Oxidative Cleavage of Alkenes |
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346 | (2) |
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8.12 Addition of Bromine and Chlorine to Alkynes |
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348 | (1) |
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8.13 Addition of Hydrogen Halides to Alkynes |
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349 | (1) |
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8.14 Oxidative Cleavage of Alkynes |
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350 | (1) |
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8.15 Synthetic Strategies Revisited |
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350 | (16) |
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The Chemistry of... Cholesterol Biosynthesis: Elegant and Familiar Reactions in Nature |
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354 | (12) |
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Chapter 9 Nuclear Magnetic Resonance and Mass Spectrometry: Tools for Structure Determination |
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366 | (63) |
| A Thermos of Liquid Helium (Molecular graphic: 1-Chloro-2-propanol) |
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366 | (1) |
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367 | (1) |
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9.2 The Electromagnetic Spectrum |
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368 | (2) |
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9.3 Nuclear Magnetic Resonance Spectroscopy |
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370 | (4) |
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9.4 Nuclear Spin: The Origin of the Signal |
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374 | (2) |
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9.5 Shielding and Deshielding of Protons |
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376 | (1) |
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377 | (2) |
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9.7 Chemical Shift Equivalent and Nonequivalent Protons |
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379 | (2) |
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9.8 Signal Splitting: Spin-Spin Coupling |
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381 | (10) |
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9.9 Proton NMR Spectra and Rate Processes |
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391 | (2) |
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9.10 Carbon-13 NMR Spectroscopy |
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393 | (4) |
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9.11 Two-Dimensional (2D) NMR Techniques |
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397 | (6) |
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The Chemistry of... Magnetic Resonance Imaging in Medicine |
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402 | (1) |
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9.12 An Introduction to Mass Spectrometry |
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403 | (1) |
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9.13 The Mass Spectrometer |
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403 | (3) |
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406 | (3) |
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9.15 Determination of Molecular Formulas and Molecular Weights |
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409 | (4) |
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413 | (7) |
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420 | (1) |
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9.18 Mass Spectrometry of Biomolecules |
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420 | (9) |
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Chapter 10 Radical Reactions |
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429 | (47) |
| Calicheamicin Gamma(1)^(1): A Radical Device for Slicing the Backbone of DNA (Molecular graphic: Calicheamicin Gamma(1)^(1), a molecule capable of double-strand DNA cleavage, bound to DNA) |
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429 | (2) |
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431 | (2) |
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The Chemistry of... Radicals in Biology, Medicine, and Industry |
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432 | (1) |
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10.2 Homolytic Bond Dissociation Energies |
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433 | (4) |
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10.3 The Reactions of Alkanes with Halogens |
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437 | (2) |
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10.4 Chlorination of Methane: Mechanism of Reaction |
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439 | (3) |
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10.5 Chlorination of Methane: Energy Changes |
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442 | (8) |
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10.6 Halogenation of Higher Alkanes |
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450 | (3) |
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10.7 The Geometry of Alkyl Radicals |
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453 | (1) |
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10.8 Reactions that Generate Tetrahedral Stereocenters |
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453 | (3) |
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10.9 Radical Addition to Alkenes: The Anti-Markovnikov Addition of Hydrogen Bromide |
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456 | (2) |
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10.10 Radical Polymerization of Alkenes: Chain-Growth Polymers |
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458 | (2) |
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10.11 Other Important Radical Reactions |
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460 | (9) |
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Special Topic A: Chain-Growth Polymers |
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469 | (7) |
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Chapter 11 Alcohols and Ethers |
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476 | (53) |
| Molecular Hosts (Molecular graphic: Monensin sodium salt, an antibiotic that transports ions across cell membranes) |
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476 | (1) |
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11.1 Structure and Nomenclature |
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477 | (3) |
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11.2 Physical Properties of Alcohols and Ethers |
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480 | (2) |
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11.3 Important Alcohols and Ethers |
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482 | (2) |
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11.4 Synthesis of Alcohols from Alkenes |
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484 | (1) |
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11.5 Alcohols from Alkenes through Oxymercuration-Demercuration |
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485 | (3) |
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11.6 Hydroboration: Synthesis of Organoboranes |
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488 | (2) |
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11.7 Alcohols from Alkenes through Hydroboration-Oxidation |
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490 | (3) |
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11.8 Reactions of Alcohols |
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493 | (1) |
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494 | (1) |
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11.10 Conversion of Alcohols into Mesylates and Tosylates |
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495 | (2) |
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11.11 Mesylates and Tosylates in S(N)2 Reactions |
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497 | (2) |
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The Chemistry of... Alkyl Phosphates |
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498 | (1) |
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11.12 Conversion of Alcohols into Alkyl Halides |
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499 | (1) |
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11.13 Alkyl Halides from the Reaction of Alcohols with Hydrogen Halides |
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499 | (3) |
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11.14 Alkyl Halides from the Reaction of Alcohols with PBr(3) or SOCI(2) |
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502 | (1) |
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11.15 Synthesis of Ethers |
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503 | (4) |
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11.16 Reactions of Ethers |
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507 | (1) |
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508 | (4) |
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The Chemistry of... The Sharpless Asymmetric Epoxidation |
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510 | (2) |
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11.18 Reactions of Epoxides |
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512 | (4) |
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The Chemistry of... Epoxides, Carcinogens, and Biological Oxidation |
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514 | (2) |
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11.19 Anti Hydroxylation of Alkenes via Epoxides |
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516 | (3) |
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11.20 Crown Ethers: Nucleophilic Substitution Reactions in Relatively Nonpolar Aprotic Solvents by Phase-Transfer Catalysis |
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519 | (4) |
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11.21 Summary of Reactions of Alkenes, Alcohols, and Ethers |
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523 | (6) |
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Chapter 12 Alcohols from Carbonyl Compounds. Oxidation-Reduction and Organometallic Compounds |
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529 | (42) |
| The Two Aspects of the Coenzyme NADH (Molecular graphic: Nicotinamide [niacin]) |
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529 | (1) |
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530 | (2) |
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12.2 Oxidation-Reduction Reactions in Organic Chemistry |
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532 | (1) |
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12.3 Alcohols by Reduction of Carbonyl Compounds |
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533 | (5) |
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The Chemistry of... Alcohol Dehydrogenase |
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536 | (1) |
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The Chemistry of... Stereoselective Reduction of Carbonyl Groups |
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537 | (1) |
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12.4 Oxidation of Alcohols |
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538 | (5) |
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12.5 Organometallic Compounds |
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543 | (1) |
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12.6 Preparation of Organolithium and Organomagnesium Compounds |
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544 | (2) |
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12.7 Reactions of Organolithium and Organomagnesium Compounds |
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546 | (3) |
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12.8 Alcohols from Grignard Reagents |
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549 | (7) |
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12.9 Lithium Dialkylcuprates: The Corey-Posner, Whitesides-House Synthesis |
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556 | (3) |
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559 | (7) |
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566 | (5) |
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Chapter 13 Conjugated Unsaturated Systems |
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571 | (48) |
| Molecules with the Nobel Prize in Their Synthetic Lineage (Molecular graphic: Morphine, the synthesis of which involved the Diels-Alder reaction) |
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571 | (1) |
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572 | (1) |
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13.2 Allylic Substitution and the Allyl Radical |
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573 | (4) |
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13.3 The Stability of the Allyl Radical |
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577 | (3) |
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580 | (2) |
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13.5 Summary of Rules for Resonance |
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582 | (4) |
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13.6 Alkadienes and Polyunsaturated Hydrocarbons |
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586 | (1) |
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13.7 1,3-Butadiene: Electron Delocalization |
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587 | (2) |
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13.8 The Stability of Conjugated Dienes |
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589 | (2) |
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13.9 Ultraviolet-Visible Spectroscopy |
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591 | (9) |
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The Chemistry of... The Photochemistry of Vision |
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596 | (4) |
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13.10 Electrophilic Attack on Conjugated Dienes: 1,4 Addition |
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600 | (4) |
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13.11 The Diels-Alder Reaction: A 1,4-Cycloaddition Reaction of Dienes |
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604 | (15) |
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Chapter 14 Aromatic Compounds |
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619 | (42) |
| Green Chemistry (Molecular graphic: Benzene, parent molecule in the family of aromatic hydrocarbons) |
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619 | (1) |
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620 | (1) |
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14.2 Nomenclature of Benzene Derivatives |
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621 | (2) |
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14.3 Reactions of Benzene |
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623 | (1) |
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14.4 The Kekule Structure for Benzene |
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624 | (2) |
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14.5 The Stability of Benzene |
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|
626 | (1) |
|
14.6 Modern Theories of the Structure of Benzene |
|
|
627 | (3) |
|
14.7 Huckel's Rule: The (4n + 2) Pi Electron Rule |
|
|
630 | (7) |
|
14.8 Other Aromatic Compounds |
|
|
637 | (5) |
|
The Chemistry of... Nanotubes |
|
|
641 | (1) |
|
14.9 Heterocyclic Aromatic Compounds |
|
|
642 | (1) |
|
14.10 Aromatic Compounds in Biochemistry |
|
|
643 | (3) |
|
14.11 Spectroscopy of Aromatic Compounds |
|
|
646 | (15) |
|
The Chemistry of... Sunscreens (Catching the Sun's Rays and What Happens to Them) |
|
|
650 | (11) |
|
Chapter 15 Reactions of Aromatic Compounds |
|
|
661 | (53) |
| Biosynthesis of Thyroxine: Aromatic Substitution Involving Iodine (Molecular graphic: Thyroxine, an aromatic iodine-containing hormone associated with regulation of metabolic rate) |
|
661 | (1) |
|
15.1 Electrophilic Aromatic Substitution Reactions |
|
|
662 | (1) |
|
15.2 A General Mechanism for Electrophilic Aromatic Substitution: Arenium Ions |
|
|
663 | (2) |
|
15.3 Halogenation of Benzene |
|
|
665 | (2) |
|
15.4 Nitration of Benzene |
|
|
667 | (1) |
|
15.5 Sulfonation of Benzene |
|
|
668 | (1) |
|
15.6 Friedel-Crafts Alkylation |
|
|
669 | (2) |
|
15.7 Friedel-Crafts Acylation |
|
|
671 | (2) |
|
15.8 Limitations of Friedel-Crafts Reactions |
|
|
673 | (2) |
|
15.9 Synthetic Applications of Friedel-Crafts Acylations: The Clemmensen Reduction |
|
|
675 | (2) |
|
15.10 Effect of Substituents on Reactivity and Orientation |
|
|
677 | (3) |
|
15.11 Theory of Substituent Effects on Electrophilic Aromatic Substitution |
|
|
680 | (12) |
|
The Chemistry of... Iodine Incorporation in Thyroxine Biosynthesis |
|
|
690 | (2) |
|
15.12 Reactions of the Side Chain of Alkylbenzenes |
|
|
692 | (4) |
|
The Chemistry of... Industrial Styrene Synthesis |
|
|
693 | (3) |
|
|
|
696 | (2) |
|
15.14 Synthetic Applications |
|
|
698 | (4) |
|
15.15 Allylic and Benzylic Halides in Nucleophilic Substitution Reactions |
|
|
702 | (2) |
|
15.16 Reduction of Aromatic Compounds |
|
|
704 | (10) |
|
Chapter 16 Aldehydes and Ketones I: Nucleophilic Addition to the Carbonyl Group |
|
|
714 | (52) |
| A Very Versatile Vitamin, Pyridoxine (Vitamin B(6)) (Molecular graphic: Pyridoxal phosphate [vitamin B(6)]) |
|
714 | (1) |
|
|
|
715 | (1) |
|
16.2 Nomenclature of Aldehydes and Ketones |
|
|
716 | (1) |
|
|
|
717 | (2) |
|
16.4 Synthesis of Aldehydes |
|
|
719 | (4) |
|
16.5 Synthesis of Ketones |
|
|
723 | (4) |
|
16.6 Nucleophilic Addition to the Carbon-Oxygen Double Bond |
|
|
727 | (3) |
|
16.7 The Addition of Alcohols: Hemiacetals and Acetals |
|
|
730 | (8) |
|
16.8 The Addition of Derivatives of Ammonia |
|
|
738 | (5) |
|
The Chemistry of... Pyridoxal Phosphate |
|
|
742 | (1) |
|
16.9 The Addition of Hydrogen Cyanide |
|
|
743 | (2) |
|
16.10 The Addition of Ylides: The Wittig Reaction |
|
|
745 | (4) |
|
16.11 The Addition of Organometallic Reagents: The Reformatsky Reaction |
|
|
749 | (1) |
|
16.12 Oxidation of Aldehydes and Ketones |
|
|
750 | (2) |
|
16.13 Chemical Analysis for Aldehydes and Ketones |
|
|
752 | (1) |
|
16.14 Spectroscopic Properties of Aldehydes and Ketones |
|
|
753 | (13) |
|
Chapter 17 Aldehydes and Ketones II. Aldol Reactions |
|
|
766 | (44) |
| TIM (Triose Phosphate Isomerase) Recycles Carbon via an Enol (Molecular graphic: Glyceraldehyde-3-phosphate, a key intermediate in metabolic energy production) |
|
766 | (1) |
|
17.1 The Acidity of the Alpha Hydrogens of Carbonyl Compounds: Enolate Anions |
|
|
767 | (2) |
|
17.2 Keto and Enol Tautomers |
|
|
769 | (1) |
|
17.3 Reactions via Enols and Enolate Anions |
|
|
770 | (6) |
|
17.4 The Aldol Reaction: The Addition of Enolate Anions to Aldehydes and Ketones |
|
|
776 | (4) |
|
17.5 Crossed Aldol Reactions |
|
|
780 | (6) |
|
17.6 Cyclizations via Aldol Condensations |
|
|
786 | (2) |
|
|
|
788 | (6) |
|
The Chemistry of... Silyl Enol Ethers |
|
|
792 | (2) |
|
17.8 Alpha-Selenation: A Synthesis of Alpha,Beta-Unsaturated Carbonyl Compounds |
|
|
794 | (1) |
|
17.9 Additions to Alpha,Beta-Unsaturated Aldehydes and Ketones |
|
|
795 | (15) |
|
The Chemistry of... Calicheamicin Gamma(1)^(I) Activation for Cleavage of DNA |
|
|
799 | (11) |
|
Chapter 18 Carboxylic Acids and Their Derivatives. Nucleophilic Addition-Elimination at the Acyl Carbon |
|
|
810 | (67) |
| A Common Bond (Molecular graphic: A portion of nylon 6, 6, a polyamide) |
|
810 | (1) |
|
|
|
811 | (1) |
|
18.2 Nomenclature and Physical Properties |
|
|
811 | (9) |
|
18.3 Preparation of Carboxylic Acids |
|
|
820 | (2) |
|
18.4 Nucleophilic Addition-Elimination at the Acyl Carbon |
|
|
822 | (3) |
|
|
|
825 | (2) |
|
18.6 Carboxylic Acid Anhydrides |
|
|
827 | (1) |
|
|
|
828 | (8) |
|
|
|
836 | (8) |
|
The Chemistry of... Penicillins |
|
|
844 | (1) |
|
18.9 Alpha-Halo Acids: The Hell-Volhard-Zelinski Reaction |
|
|
844 | (2) |
|
18.10 Derivatives of Carbonic Acid |
|
|
846 | (3) |
|
18.11 Decarboxylation of Carboxylic Acids |
|
|
849 | (2) |
|
The Chemistry of... Thiamine |
|
|
850 | (1) |
|
18.12 Chemical Tests for Acyl Compounds |
|
|
851 | (17) |
|
Special Topic B: Step-Growth Polymers |
|
|
868 | (9) |
|
Chapter 19 Synthesis and Reactions of Beta-Dicarbonyl Compounds: More Chemistry of Enolate Ions |
|
|
877 | (65) |
| Imposters (Molecular graphic: 5-Fluorouracil, an enzyme inhibitor that has anticancer activity by masquerading as a natural substrate) |
|
877 | (1) |
|
|
|
878 | (1) |
|
19.2 The Claisen Condensation: The Synthesis of Beta-Keto Esters |
|
|
879 | (6) |
|
19.3 The Acetoacetic Ester Synthesis: Synthesis of Methyl Ketones (Substituted Acetones) |
|
|
885 | (7) |
|
19.4 The Malonic Ester Synthesis: Synthesis of Substituted Acetic Acids |
|
|
892 | (4) |
|
19.5 Further Reactions of Active Hydrogen Compounds |
|
|
896 | (1) |
|
19.6 Direct Alkylation of Esters and Nitriles |
|
|
897 | (1) |
|
19.7 Alkylation of 1,3-Dithianes |
|
|
898 | (2) |
|
19.8 The Knoevenagel Condensation |
|
|
900 | (1) |
|
|
|
900 | (2) |
|
The Chemistry of... A Suicide Enzyme Substrate |
|
|
902 | (1) |
|
19.10 The Mannich Reaction |
|
|
902 | (2) |
|
19.11 Synthesis of Enamines: Stork Enamine Reactions |
|
|
904 | (4) |
|
|
|
908 | (15) |
|
The Chemistry of... Antibody-Catalyzed Aldol Condensations |
|
|
909 | (14) |
|
Special Topic C: Thiols, Sulfur Ylides, and Disulfides |
|
|
923 | (5) |
|
Special Topic D: Thiol Esters and Lipid Biosynthesis |
|
|
928 | (14) |
|
|
|
942 | (72) |
| Neurotoxins and Neurotransmitters (Molecular graphic: Histrionicatoxin, a paralyzing neurotoxin from certain poison dart frogs) |
|
942 | (2) |
|
|
|
944 | (1) |
|
20.2 Physical Properties and Structure of Amines |
|
|
945 | (2) |
|
20.3 Basicity of Amines: Amine Salts |
|
|
947 | (8) |
|
The Chemistry of... HPLC Resolution of Enantiomers |
|
|
954 | (1) |
|
20.4 Some Biologically Important Amines |
|
|
955 | (2) |
|
20.5 Preparation of Amines |
|
|
957 | (8) |
|
|
|
965 | (1) |
|
20.7 Reactions of Amines with Nitrous Acid |
|
|
966 | (3) |
|
The Chemistry of... N-Nitrosoamines |
|
|
968 | (1) |
|
20.8 Replacement Reactions of Arenediazonium Salts |
|
|
969 | (3) |
|
20.9 Coupling Reactions of Arenediazonium Salts |
|
|
972 | (3) |
|
20.10 Reactions of Amines with Sulfonyl Chlorides |
|
|
975 | (2) |
|
20.11 The Sulfa Drugs: Sulfanilamide |
|
|
977 | (3) |
|
|
|
980 | (2) |
|
20.13 Eliminations Involving Ammonium Compounds |
|
|
982 | (15) |
|
Special Topic E: Reactions and Synthesis of Heterocyclic Amines |
|
|
997 | (11) |
|
Special Topic F: Alkaloids |
|
|
1008 | (6) |
|
Chapter 21 Phenols and Aryl Halides: Nucleophilic Aromatic Substitution |
|
|
1014 | (74) |
| A Silver Chalice (Molecular graphic: 4-tert-Butylcalix[4]arene, a chalice-shaped molecule) |
|
1014 | (1) |
|
21.1 Structure and Nomenclature of Phenols |
|
|
1015 | (1) |
|
21.2 Naturally Occurring Phenols |
|
|
1016 | (3) |
|
The Chemistry of... Polyketide Anticancer Antibiotic Biosynthesis |
|
|
1017 | (2) |
|
21.3 Physical Properties of Phenols |
|
|
1019 | (1) |
|
21.4 Synthesis of Phenols |
|
|
1019 | (4) |
|
21.5 Reactions of Phenols as Acids |
|
|
1023 | (2) |
|
21.6 Other Reactions of the O--H Group of Phenols |
|
|
1025 | (1) |
|
21.7 Cleavage of Alkyl Aryl Ethers |
|
|
1026 | (1) |
|
21.8 Reactions of the Benzene Ring of Phenols |
|
|
1027 | (2) |
|
21.9 The Claisen Rearrangement |
|
|
1029 | (1) |
|
|
|
1030 | (2) |
|
21.11 Aryl Halides and Nucleophilic Aromatic Substitution |
|
|
1032 | (7) |
|
The Chemistry of... Bacterial Dehalogenation of a PCB Derivative |
|
|
1035 | (4) |
|
21.12 Spectroscopic Analysis of Phenols and Aryl Halides |
|
|
1039 | (11) |
|
Second Review Problem Set |
|
|
1050 | (38) |
|
Special Topic G: Electrocyclic and Cycloaddition Reactions |
|
|
1056 | (15) |
|
Special Topic H: Organic Halides and Organometallic Compounds in the Environment |
|
|
1071 | (6) |
|
Special Topic I: Transition Metal Organometallic Compounds |
|
|
1077 | (11) |
|
|
|
1088 | (54) |
| Carbohydrate Recognition in Healing and Disease (Molecular graphic: Sialyl Lewis,^(x) a carbohydrate that is important in the recognition and healing of traumatized tissue) |
|
1088 | (1) |
|
|
|
1089 | (3) |
|
|
|
1092 | (6) |
|
|
|
1098 | (1) |
|
|
|
1099 | (3) |
|
22.5 Other Reactions of Monosaccharides |
|
|
1102 | (2) |
|
22.6 Oxidation Reactions of Monosaccharides |
|
|
1104 | (6) |
|
22.7 Reduction of Monosaccharides: Alditols |
|
|
1110 | (1) |
|
22.8 Reactions of Monosaccharides with Phenylhydrazine: Osazones |
|
|
1110 | (2) |
|
22.9 Synthesis and Degradation of Monosaccharides |
|
|
1112 | (2) |
|
22.10 The D Family of Aldoses |
|
|
1114 | (1) |
|
22.11 Fischer's Proof of the Configuration of D-(+)-Glucose |
|
|
1114 | (4) |
|
|
|
1118 | (5) |
|
The Chemistry of... Artificial Sweeteners (How Sweet It Is) |
|
|
1122 | (1) |
|
|
|
1123 | (5) |
|
22.14 Other Biologically Important Sugars |
|
|
1128 | (1) |
|
22.15 Sugars that Contain Nitrogen |
|
|
1129 | (1) |
|
22.16 Glycolipids and Glycoproteins of the Cell Surface |
|
|
1130 | (2) |
|
22.17 Carbohydrate Antibiotics |
|
|
1132 | (10) |
|
|
|
1142 | (37) |
| Insulation for Nerves (Molecular graphic: A sphingomyelin molecule, found in myelin sheath membranes) |
|
1142 | (1) |
|
|
|
1143 | (1) |
|
23.2 Fatty Acids and Triacylglycerols |
|
|
1144 | (8) |
|
The Chemistry of... Olestra and Other Fat Substitutes |
|
|
1148 | (4) |
|
23.3 Terpenes and Terpenoids |
|
|
1152 | (4) |
|
|
|
1156 | (9) |
|
|
|
1165 | (2) |
|
23.6 Phospholipids and Cell Membranes |
|
|
1167 | (3) |
|
|
|
1170 | (9) |
|
Chapter 24 Amino Acids and Proteins |
|
|
1179 | (49) |
| Catalytic Antibodies: Designer Catalysts (Molecular graphic: A synthetic Diels-alderase catalytic antibody with a bound hapten) |
|
1179 | (1) |
|
|
|
1180 | (1) |
|
|
|
1181 | (5) |
|
24.3 Laboratory Synthesis of Alpha-Amino Acids |
|
|
1186 | (4) |
|
24.4 Analysis of Polypeptides and Proteins |
|
|
1190 | (3) |
|
24.5 Amino Acid Sequence of Polypeptides and Proteins |
|
|
1193 | (3) |
|
24.6 Primary Structure of Polypeptides and Proteins |
|
|
1196 | (4) |
|
The Chemistry of... Sickle Cell Anemia |
|
|
1199 | (1) |
|
24.7 Polypeptide and Protein Synthesis |
|
|
1200 | (5) |
|
24.8 Secondary, Tertiary, and Quaternary Structure of Proteins |
|
|
1205 | (7) |
|
24.9 Introduction to Enzymes |
|
|
1212 | (1) |
|
24.10 Lysozyme: Mode of Action of an Enzyme |
|
|
1213 | (2) |
|
|
|
1215 | (7) |
|
The Chemistry of... Some Catalytic Antibodies |
|
|
1220 | (2) |
|
24.12 Hemoglobin: A Conjugated Protein |
|
|
1222 | (6) |
|
Chapter 25 Nucleic Acids and Protein Synthesis |
|
|
1228 | |
| Tools for Finding Families (Molecular graphic: A cytosine-guanine base pair, depicting the van der Waals surface as an electrostatic patential map) |
|
1228 | (1) |
|
|
|
1229 | (1) |
|
25.2 Nucleotides and Nucleosides |
|
|
1229 | (3) |
|
25.3 Laboratory Synthesis of Nucleosides and Nucleotides |
|
|
1232 | (4) |
|
25.4 Deoxyribonucleic Acid: DNA |
|
|
1236 | (7) |
|
25.5 RNA and Protein Synthesis |
|
|
1243 | (7) |
|
25.6 Determining the Base Sequence of DNA |
|
|
1250 | (3) |
|
25.7 Laboratory Synthesis of Oligonucleotides |
|
|
1253 | (2) |
|
25.8 The Polymerase Chain Reaction |
|
|
1255 | |
| Answers to Selected Problems |
|
A1 | |
| Glossary |
|
G1 | |
|
Illustration and Photo Credits |
|
|
C1 | |
| Index |
|
I1 | |
Other versions by this Author