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List of Biochemistry Topics |
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xxix | |
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xxx | |
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List of Connections Boxes |
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xxxi | |
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List of Green Chemistry Boxes |
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xxxiii | |
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xxxiv | |
| Preface |
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xxxviii | |
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1 Atomic and Molecular Structure |
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1 | (51) |
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1.1 What Is Organic Chemistry? |
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1 | (2) |
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3 | (1) |
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1.3 Atomic Structure and Ground State Electron Configurations |
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4 | (4) |
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1.4 The Covalent Bond: Bond Energy and Bond Length |
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8 | (3) |
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1.5 Lewis Dot Structures and the Octet Rule |
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11 | (3) |
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1.6 Strategies for Success: Drawing Lewis Dot Structures Quickly |
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14 | (1) |
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1.7 Electronegativity, Polar Covalent Bonds, and Bond Dipoles |
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15 | (3) |
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18 | (2) |
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1.9 Assigning Electrons to Atoms in Molecules: Formal Charge |
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20 | (1) |
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21 | (5) |
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1.11 Strategies for Success: Drawing All Resonance Structures |
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26 | (4) |
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30 | (3) |
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1.13 An Overview of Organic Compounds: Functional Groups |
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33 | (4) |
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The Organic Chemistry of Biomolecules |
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1.14 An Introduction to Proteins, Carbohydrates, and Nucleic Acids: Fundamental Building Blocks and Functional Groups |
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37 | (15) |
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Chapter Summary and Key Terms |
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44 | (1) |
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44 | (8) |
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A Nomenclature: The Basic System for Naming Organic Compounds Alkanes, Haloalkanes, Nitroalkanes, Cycloalkanes, and Ethers |
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52 | (16) |
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A.1 The Need for Systematic Nomenclature: An Introduction to the IUPAC System |
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52 | (1) |
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A.2 Alkanes and Substituted Alkanes |
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53 | (2) |
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A.3 Haloalkanes and Nitroalkanes: Roots, Prefixes, and Locator Numbers |
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55 | (4) |
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A.4 Alkyl Substituents: Branched Alkanes and Substituted Branched Alkanes |
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59 | (2) |
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A.5 Cyclic Alkanes and Cyclic Alkyl Groups |
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61 | (2) |
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A.6 Ethers and Alkoxy Groups |
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63 | (1) |
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A.7 Trivial Names or Common Names |
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64 | (1) |
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65 | (3) |
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2 Three-Dimensional Geometry, Intermolecular Interactions, and Physical Properties |
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68 | (44) |
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2.1 Valence Shell Electron Pair Repulsion (VSEPR) Theory: Three-Dimensional Geometry |
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69 | (4) |
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73 | (2) |
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2.3 Strategies for Success: The Molecular Modeling Kit |
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75 | (1) |
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2.4 Net Molecular Dipoles |
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76 | (1) |
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2.5 Physical Properties, Functional Groups, and Intermolecular Interactions |
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77 | (2) |
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2.6 Melting Points, Boiling Points, and Intermolecular Interactions |
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79 | (8) |
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87 | (5) |
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2.8 Strategies for Success: Ranking Boiling Points and Solubilities of Structurally Similar Compounds |
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92 | (4) |
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2.9 Protic and Aprotic Solvents |
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96 | (2) |
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The Organic Chemistry of Biomolecules |
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2.10 An Introduction to Lipids |
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98 | (14) |
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Chapter Summary and Key Terms |
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104 | (1) |
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105 | (7) |
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3 Valence Bond Theory and Molecular Orbital Theory |
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112 | (38) |
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3.1 An Introduction to Valence Bond Theory and σ Bonds: An Example with H2 |
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113 | (2) |
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3.2 Valence Bond Theory and Tetrahedral Electron Geometry: Alkanes and sp3 Hybridization |
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115 | (3) |
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3.3 Valence Bond Theory and Lone Pairs of Electrons |
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118 | (2) |
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3.4 Valence Bond Theory and Trigonal Planar Electron Geometry: Double Bonds, sp2 Hybridization, it Bonds, and Carbocations |
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120 | (4) |
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3.5 Valence Bond Theory and Linear Electron Geometry: Triple Bonds and sp Hybridization |
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124 | (3) |
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3.6 Strategies for Success: Quickly Identifying Hybridization and the Number of σ and π Bonds from a Lewis Structure |
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127 | (2) |
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3.7 Bond Rotations about Single and Double Bonds: Cis and Trans Configurations |
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129 | (3) |
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3.8 Strategies for Success: Molecular Modeling Kits, Bond Rotations, and Extended Geometries |
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132 | (1) |
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3.9 Hybridization, Bond Characteristics, and Effective Electronegativity |
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133 | (3) |
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3.10 A Deeper Look: Molecular Orbital Theory and the Wave Nature of Electrons |
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136 | (4) |
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3.11 A Deeper Look: Hybrid Atomic Orbitals and a Combined Molecular Orbital-Valence Bond Model |
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140 | (10) |
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Chapter Summary and Key Terms |
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145 | (1) |
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146 | (4) |
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B Naming Alkenes, Alkynes, and Benzene Derivatives |
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150 | (12) |
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B.1 Alkenes, Alkynes, Cycloalkenes, and Cycloalkynes: Molecules with One C C or C C Bond |
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150 | (3) |
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B.2 Molecules with Multiple C C or C C Bonds |
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153 | (2) |
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B.3 Benzene and Benzene Derivatives |
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155 | (3) |
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158 | (4) |
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4 Isomerism 1 Conformers and Constitutional Isomers |
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162 | (43) |
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4.1 Conformers: Rotational Conformations, Newman Projections, and Dihedral Angles |
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163 | (2) |
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4.2 Conformers: Energy Changes and Conformational Analysis |
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165 | (5) |
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4.3 Conformers: Ring Strain and the Most Stable Conformations of Cyclic Alkanes |
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170 | (3) |
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4.4 A Deeper Look: Calculating Ring Strain from Heats of Combustion |
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173 | (2) |
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4.5 Conformers: Cyclohexane and Chair Flips |
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175 | (2) |
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4.6 Strategies for Success: Drawing Chair Conformations of Cyclohexane |
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177 | (2) |
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4.7 Conformers: Monosubstituted Cyclohexanes |
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179 | (3) |
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4.8 Conformers: Disubstituted Cyclohexanes, Cis and Trans Isomers, and Haworth Projections |
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182 | (3) |
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4.9 Strategies for Success: Molecular Modeling Kits and Chair Flips |
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185 | (1) |
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4.10 Constitutional Isomerism: Identifying Constitutional Isomers |
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185 | (2) |
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4.11 Constitutional Isomers: Index of Hydrogen Deficiency (Degree of Unsaturation) |
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187 | (4) |
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4.12 Strategies for Success: Drawing All Constitutional Isomers of a Given Formula |
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191 | (4) |
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The Organic Chemistry of Biomolecules |
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4.13 Constitutional Isomers and Biomolecules: Amino Acids and Monosaccharides |
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195 | (1) |
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4.14 Saturation and Unsaturation in Fats and Oils |
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196 | (9) |
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Chapter Summary and Key Terms |
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198 | (1) |
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199 | (6) |
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5 Isomerism 2 Chirality, Enantiomers, and Diastereomers |
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205 | (59) |
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5.1 Defining Configurational Isomers, Enantiomers, and Diastereomers |
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205 | (2) |
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5.2 Enantiomers, Mirror Images, and Superimposability |
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207 | (2) |
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5.3 Strategies for Success: Drawing Mirror Images |
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209 | (2) |
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5.4 Chirality and the Plane of Symmetry Test |
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211 | (2) |
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213 | (6) |
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5.6 Absolute Stereochemical Configurations: R/S Designations of Chiral Centers |
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219 | (6) |
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5.7 Mirror Images That Rapidly Interconvert: Single-Bond Rotation and Nitrogen Inversion |
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225 | (3) |
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5.8 Diastereomers: Double-Bond Configurations and Chiral Centers |
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228 | (4) |
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5.9 Strategies for Success: Drawing All Stereoisomers of a Molecule with Chiral Centers |
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232 | (3) |
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5.10 Fischer Projections and Stereochemistry |
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235 | (2) |
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5.11 Strategies for Success: Converting between Fischer Projections and Zigzag Conformations |
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237 | (3) |
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5.12 Physical and Chemical Properties of Isomers |
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240 | (4) |
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5.13 Separating Configurational Isomers |
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244 | (1) |
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245 | (4) |
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The Organic Chemistry of Biomolecules |
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5.15 The Chirality of Biomolecules |
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249 | (1) |
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5.16 The D/L System for Classifying Monosaccharides and Amino Acids |
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250 | (1) |
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5.17 The D Family of Aldoses |
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251 | (13) |
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Chapter Summary and Key Terms |
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253 | (1) |
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254 | (10) |
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6 The Proton Transfer Reaction An Introduction to Mechanisms, Equilibria, Free Energy Diagrams, and Charge Stability |
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264 | (54) |
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6.1 An Introduction to Reaction Mechanisms: The Proton Transfer Reaction and Curved Arrow Notation |
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265 | (2) |
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6.2 Proton Transfer Reaction Outcomes: pKa Values and Acid and Base Strengths |
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267 | (9) |
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6.3 A Deeper Look: Chemical Equilibrium, Equilibrium Constants, and Ka Values |
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276 | (3) |
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6.4 Gibbs Free Energy and the Reaction Free Energy Diagram |
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279 | (1) |
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6.5 A Deeper Look: Gibbs Free Energy, Equilibrium Constants, Enthalpy, and Entropy |
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280 | (2) |
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6.6 Functional Groups and Acidity |
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282 | (1) |
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6.7 Relative Strengths of Charged and Uncharged Acids: The Reactivity of Charged Species |
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283 | (2) |
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6.8 Relative Acidities of Protons on Atoms with Like Charges |
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285 | (14) |
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6.9 Strategies for Success: Ranking Acid and Base Strengths by Using the CARDIN-al Rule |
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299 | (4) |
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The Organic Chemistry of Biomolecules |
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6.10 The Structure of Amino Acids in Solution as a Function of pH |
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303 | (15) |
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Chapter Summary and Key Terms |
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306 | (1) |
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307 | (11) |
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7 An Overview of the Most Common Elementary Steps |
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318 | (42) |
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7.1 Mechanisms as Predictive Tools: The Proton Transfer Step Revisited |
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319 | (6) |
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7.2 Bimolecular Nucleophilic Substitution (SN2) Steps |
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325 | (4) |
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7.3 Bond-Forming (Coordination) and Bond-Breaking (Heterolysis) Steps |
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329 | (2) |
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7.4 Nucleophilic Addition and Nucleophile Elimination Steps |
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331 | (2) |
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7.5 Bimolecular Elimination (E2) Steps |
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333 | (2) |
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7.6 Electrophilic Addition and Electrophile Elimination Steps |
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335 | (3) |
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7.7 Carbocation Rearrangements: 1,2-Hydride Shifts and 1,2-Alkyl Shifts |
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338 | (1) |
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7.8 The Driving Force for Chemical Reactions |
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339 | (2) |
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7.9 Carbocations and Charge Stability |
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341 | (4) |
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7.10 Keto--Enol Tautomerization: An Example of Bond Energies as the Major Driving Force |
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345 | (15) |
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Chapter Summary and Key Terms |
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350 | (1) |
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351 | (9) |
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C Molecular Orbital Theory and Chemical Reactions |
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360 | (11) |
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C.1 An Overview of Frontier Molecular Orbital Theory |
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360 | (3) |
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C.2 Frontier Molecular Orbital Theory and Elementary Steps |
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363 | (7) |
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370 | (1) |
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D Naming Compounds with a Functional Group That Calls for a Suffix: Alcohols, Amines, Ketones, Aldehydes, Carboxylic Acids, and Carboxylic Acid Derivatives |
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371 | (22) |
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D.1 The Basic System for Naming Compounds with a Functional Group That: Calls for a Suffix |
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372 | (1) |
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D.2 Naming Alcohols and Amines |
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372 | (7) |
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D.3 Naming Ketones and Aldehydes |
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379 | (2) |
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D.4 Naming Carboxylic Acids, Acid Chlorides, Amides, and Nitriles |
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381 | (4) |
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D.5 Naming Esters and Acid Anhydrides |
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385 | (4) |
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389 | (4) |
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8 An Introduction to Multistep Mechanisms SN1 and El Reactions and Their Comparisons to SN2 and E2 Reactions |
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393 | (51) |
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8.1 The Unimolecular Nucleophilic Substitution (SN1) Reaction: Intermediates, Overall Reactants, and Overall Products |
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394 | (3) |
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8.2 The Unimolecular Elimination (El) Reaction |
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397 | (2) |
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8.3 The Kinetics of SN2, SN1, E2, and El Reactions: Evidence for Reaction Mechanisms |
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399 | (5) |
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8.4 A Deeper Look: Theoretical Rate Laws and Transition State Theory |
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404 | (2) |
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8.5 Stereochemistry of Nucleophilic Substitution and Elimination Reactions |
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406 | (16) |
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8.6 The Reasonableness of a Mechanism: Proton Transfers and Carbocation Rearrangements |
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422 | (12) |
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8.7 Resonance-Delocalized Intermediates in Mechanisms |
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434 | (10) |
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Chapter Summary and Key Terms |
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436 | (1) |
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436 | (8) |
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9 Competition among SN2, SN1, E2, and El Reactions |
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444 | (64) |
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9.1 Identifying the Competition among SN2, SN1, E2, and El Reactions |
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445 | (2) |
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9.2 Rate-Determining Steps Revisited: Simplified Pictures of SN2, SN1, E2, and El Reactions |
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447 | (1) |
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9.3 Factor 1: Strength of the Attacking Species |
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448 | (10) |
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9.4 Factor 2: Concentration of the Attacking Species |
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458 | (2) |
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9.5 Factor 3: Leaving Group Ability |
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460 | (6) |
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9.6 Factor 4: Type of Carbon Bonded to the Leaving Group |
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466 | (7) |
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9.7 Factor 5: Solvent Effects |
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473 | (6) |
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479 | (2) |
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9.9 Strategies for Success: Predicting the Outcome of an SN2/SN1/E2/E1 Competition |
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481 | (6) |
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9.10 Regioselectivity in Elimination Reactions: Alkene Stability and Zaitsev's Rule |
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487 | (3) |
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9.11 A Deeper Look: Hyperconjugation and Alkene Stability |
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490 | (1) |
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9.12 Intermolecular Reactions versus Intramolecular Cyclizations |
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491 | (3) |
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The Organic Chemistry of Biomolecules |
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9.13 Nucleophilic Substitution Reactions and Monosaccharides: The Formation and Hydrolysis of Glycosides |
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494 | (14) |
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Chapter Summary and Key Terms |
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497 | (1) |
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498 | (2) |
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500 | (8) |
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10 Organic Synthesis 1 Nucleophilic Substitution and Elimination Reactions and Functional Group Transformations |
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508 | (54) |
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10.1 The Language of Organic Synthesis |
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509 | (1) |
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10.2 Writing the Reactions of an Organic Synthesis |
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510 | (4) |
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10.3 Cataloging Reactions: Functional Group Transformations and Carbon--Carbon Bond-Forming and Bond-Breaking Reactions |
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514 | (3) |
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10.4 Options and Limitations in Synthesis: Ether Formation by the Williamson Synthesis and Condensation |
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517 | (6) |
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10.5 Converting Alcohols into Alkyl Halides: PBr3 and PCI3 |
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523 | (4) |
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10.6 Halogenation of a Carbons |
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527 | (7) |
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10.7 Epoxides as Substrates |
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534 | (5) |
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10.8 Formation of Epoxides by Nucleophilic Substitution |
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539 | (2) |
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10.9 Diazomethane Formation of Methyl Esters |
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541 | (1) |
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10.10 Amines and Quaternary Ammonium Salts from Alkyl Halides |
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542 | (3) |
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10.11 Hofmann Elimination |
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545 | (3) |
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10.12 Generating Alkynes by Elimination Reactions |
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548 | (14) |
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Chapter Summary and Key Terms |
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551 | (1) |
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552 | (2) |
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554 | (8) |
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11 Organic Synthesis 2 Reactions That Alter the Carbon Skeleton, and Designing Multistep Syntheses |
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562 | (42) |
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11.1 Reactions That Alter the Carbon Skeleton and Retrosynthetic Analysis |
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563 | (7) |
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11.2 Carbon Nucleophiles and the Opening of Epoxides |
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570 | (3) |
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11.3 Alkylation of a Carbons: Regioselectivity and Kinetic versus Thermodynamic Control |
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573 | (8) |
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581 | (4) |
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11.5 Strategies for Success: Improving Your Proficiency with Solving Multistep Syntheses |
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585 | (2) |
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587 | (3) |
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11.7 A Deeper Look: Considerations of Percent Yield |
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590 | (14) |
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Chapter Summary and Key Terms |
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594 | (1) |
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595 | (1) |
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596 | (8) |
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12 Electrophilic Addition to Nonpolar Bonds 1 Addition of a Brønsted Acid |
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604 | (43) |
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12.1 The General Electrophilic Addition Mechanism: Addition of a Strong Brønsted Acid to an Alkene |
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606 | (3) |
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12.2 Benzene Rings Do Not Readily Undergo Electrophilic Addition of Brønsted Acids |
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609 | (1) |
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12.3 Regiochemistry: Production of the More Stable Carbocation and Markovnikov's Rule |
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610 | (3) |
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12.4 Carbocation Rearrangements |
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613 | (2) |
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12.5 Stereochemistry in the Addition of a Brønsted Acid to an Alkene |
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615 | (1) |
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12.6 Addition of a Weak Acid: Acid Catalysis |
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616 | (4) |
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12.7 Electrophilic Addition of a Strong Brensted Acid to an Alkyne |
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620 | (3) |
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12.8 Acid-Catalyzed Hydration of an Alkyne: Synthesis of a Ketone |
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623 | (1) |
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12.9 Electrophilic Addition of a Brønsted Acid to a Conjugated Diene: 1,2-Addition and 1,4-Addition |
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624 | (4) |
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12.10 Kinetic versus Thermodynamic Control in Electrophilic Addition to a Conjugated Diene |
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628 | (3) |
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12.11 Organic Synthesis: Additions of Brønsted Acids to Alkenes and Alkynes |
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631 | (3) |
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The Organic Chemistry of Biomolecules |
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12.12 Terpenes and Their Biosynthesis: Carbocation Chemistry in Nature |
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634 | (13) |
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Chapter Summary and Key Terms |
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638 | (1) |
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639 | (1) |
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640 | (7) |
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13 Electrophilic Addition to Nonpolar π Bonds 2 Reactions Involving Cyclic Transition States |
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647 | (46) |
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13.1 Electrophilic Addition via a Three-Membered Ring: The General Mechanism |
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648 | (2) |
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13.2 Electrophilic Addition of Carbenes: Formation of Cyclopropane Rings |
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650 | (1) |
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13.3 Epoxide Formation with Peroxy Acids |
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651 | (3) |
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13.4 Electrophilic Addition Involving Molecular Halogens: Synthesis of 1,2-Dihalides and Halohydrins |
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654 | (7) |
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13.5 Oxymercuration--Reduction: Addition of Water |
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661 | (6) |
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13.6 Hydroboration--Oxidation: Anti-Markovnikov Syn Addition of Water to an Alkene |
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667 | (7) |
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13.7 Hydroboration--Oxidation of Alkynes |
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674 | (1) |
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13.8 Organic Synthesis: Using Electrophilic Addition Reactions That Proceed through a Cyclic Transition State |
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675 | (3) |
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13.9 Organic Synthesis: Catalytic Hydrogenation of Alkenes and Alkynes |
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678 | (15) |
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Chapter Summary and Key Terms |
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684 | (1) |
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685 | (2) |
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687 | (6) |
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14 Conjugation and Aromaticity |
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693 | (46) |
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14.1 The Allyl Cation and Buta-1,3-diene: Resonance and the Conjugation of p Orbitals in Acyclic π Systems |
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694 | (4) |
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698 | (2) |
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14.3 A Deeper Look: Heats of Hydrogenation and the Stability of Conjugated π Bonds |
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700 | (2) |
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14.4 The Allyl Anion: Conjugation and Lone Pairs of Electrons |
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702 | (2) |
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14.5 Cyclic π Systems: Benzene as an Aromatic Compound, and Cyclobutadiene as an Antiaromatic Compound |
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704 | (2) |
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14.6 A Deeper Look: Using Heats of Hydrogenation to Determine Aromaticity |
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706 | (3) |
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14.7 Huckel's Rules: Assessing Aromaticity Using Lewis Structures |
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709 | (6) |
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14.8 A Deeper Look: Molecular Orbital Theory, Conjugation, and Aromaticity |
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715 | (13) |
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The Organic Chemistry of Biomolecules |
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728 | (11) |
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Chapter Summary and Key Terms |
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732 | (1) |
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733 | (6) |
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15 Structure Determination 1 Mass Spectrometry |
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739 | (30) |
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15.1 An Overview of Mass Spectrometry |
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740 | (2) |
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15.2 Features of a Mass Spectrum, the Nitrogen Rule, and Fragmentation |
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742 | (3) |
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15.3 Isotopes and Mass Spectra: M + 1 and M + 2 Peaks |
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745 | (4) |
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15.4 A Deeper Look: Estimating the Number of Carbon Atoms from the M + 1 Peak |
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749 | (2) |
|
15.5 Strategies for Success: Determining a Molecular Formula from the Mass Spectrum of an Organic Compound |
|
|
751 | (2) |
|
15.6 A Deeper Look: Fragmentation Pathways in Mass Spectrometry |
|
|
753 | (16) |
|
Chapter Summary and Key Terms |
|
|
764 | (1) |
|
|
|
764 | (5) |
|
16 Structure Determination 2 Infrared Spectroscopy and Ultraviolet-Visible Spectroscopy |
|
|
769 | (50) |
|
16.1 An Overview of Infrared Spectroscopy |
|
|
770 | (2) |
|
16.2 General Theory of Infrared Spectroscopy |
|
|
772 | (2) |
|
16.3 Location of Peaks in an Infrared Spectrum |
|
|
774 | (4) |
|
16.4 The Ball-and-Spring Model for Explaining Infrared Peak Locations |
|
|
778 | (3) |
|
16.5 Intensities of Peaks in an Infrared Spectrum |
|
|
781 | (2) |
|
16.6 Some Important Infrared Stretches |
|
|
783 | (9) |
|
16.7 Strategies for Success: Structure Elucidation Using Infrared Spectroscopy |
|
|
792 | (6) |
|
16.8 A Deeper Look: Infrared Bending Vibrations |
|
|
798 | (2) |
|
16.9 An Overview of Ultraviolet--Visible Spectroscopy |
|
|
800 | (1) |
|
16.10 Ultraviolet--Visible Spectra and Molecular Structure: Conjugation and Lone Pairs |
|
|
801 | (5) |
|
16.11 A Deeper Look: Molecular Orbital Theory and Ultraviolet--Visible Spectroscopy |
|
|
806 | (13) |
|
Chapter Summary and Key Terms |
|
|
809 | (1) |
|
|
|
810 | (9) |
|
17 Structure Determination 3 Nuclear Magnetic Resonance Spectroscopy |
|
|
819 | (59) |
|
17.1 An Overview of Nuclear Magnetic Resonance Spectroscopy |
|
|
819 | (2) |
|
17.2 Nuclear Spin and the Nuclear Magnetic Resonance Signal |
|
|
821 | (2) |
|
17.3 Shielding, Chemical Distinction, and the Number of NMR Signals |
|
|
823 | (7) |
|
17.4 The Time Scale of Nuclear Magnetic Resonance Spectroscopy |
|
|
830 | (1) |
|
17.5 Characteristic Chemical Shifts, Inductive Effects, and Magnetic Anisotropy |
|
|
831 | (4) |
|
17.6 Strategies for Success: Predicting Approximate Chemical Shift Values |
|
|
835 | (3) |
|
17.7 A Deeper Look: A Quantitative Examination of the NMR Signal and Chemical Shift and a Look at Deuterated Solvents |
|
|
838 | (2) |
|
17.8 Integration of Signals |
|
|
840 | (1) |
|
17.9 Splitting of the Signal by Spin-Spin Coupling: The N + 1 Rule |
|
|
841 | (6) |
|
17.10 Coupling Constants and Complex Signal Splitting |
|
|
847 | (4) |
|
17.11 A Deeper Look: Signal Resolution and the Strength of Bext |
|
|
851 | (2) |
|
17.12 Carbon Signals: 13C Nuclear Magnetic Resonance Spectroscopy |
|
|
853 | (5) |
|
17.13 A Deeper Look: DEPT 13C NMR Spectroscopy and 2-D NMR Spectra |
|
|
858 | (2) |
|
17.14 Strategies for Success: Elucidating Molecular Structure Using Nuclear Magnetic Resonance Spectroscopy |
|
|
860 | (18) |
|
Chapter Summary and Key Terms |
|
|
867 | (1) |
|
|
|
868 | (10) |
|
18 Nucleophilic Addition to Polar π Bonds 1 Reagents That Are Strongly Nucleophilic |
|
|
878 | (48) |
|
18.1 An Overview of the General Mechanism: Addition of Strong Nucleophiles |
|
|
879 | (2) |
|
18.2 Substituent Effects: Relative Reactivity of Ketones and Aldehydes in Nucleophilic Addition |
|
|
881 | (2) |
|
18.3 Reactions of Hydride Reagents: LiAIH4, NaBH4, and NaH |
|
|
883 | (7) |
|
18.4 Reactions of Organometallic Compounds: Alkyllithium Reagents and Grignard Reagents |
|
|
890 | (4) |
|
18.5 Compatibility of Functional Groups in Reactions Involving Alkyllithium and Grignard Reagents |
|
|
894 | (1) |
|
18.6 Wittig Reagents and the Wittig Reaction: Synthesis of Alkenes |
|
|
895 | (2) |
|
18.7 Generating Wittig Reagents |
|
|
897 | (3) |
|
18.8 Direct Addition versus Conjugate Addition |
|
|
900 | (5) |
|
18.9 Lithium Dialkylcuprates and the Selectivity of Organometallic Reagents |
|
|
905 | (3) |
|
18.10 Organic Synthesis: Grignard and Alkyllithium Reactions in Synthesis |
|
|
908 | (2) |
|
18.11 Organic Synthesis: Considerations of Direct Addition versus Conjugate Addition |
|
|
910 | (2) |
|
18.12 Organic Synthesis: Considerations of Regiochemistry in the Formation of Alkenes |
|
|
912 | (14) |
|
Chapter Summary and Key Terms |
|
|
914 | (1) |
|
|
|
915 | (2) |
|
|
|
917 | (9) |
|
19 Nucleophilic Addition to Polar π Bonds 2 Reagents That Are Weakly Nucleophilic or Non-nucleophilic, and Acid and Base Catalysis |
|
|
926 | (61) |
|
19.1 Weak Nucleophiles as Reagents: Acid and Base Catalysis |
|
|
926 | (5) |
|
19.2 Addition of HCN: The Formation of Cyanohydrins |
|
|
931 | (2) |
|
19.3 Direct Addition versus Conjugate Addition of Weak Nucleophiles and HCN |
|
|
933 | (2) |
|
19.4 Formation and Hydrolysis of Acetals, Imines, and Enamines |
|
|
935 | (9) |
|
19.5 Organic Synthesis: Synthesizing Amines via Reductive Amination |
|
|
944 | (2) |
|
19.6 The Wolff--Kishner Reduction |
|
|
946 | (1) |
|
19.7 Hydrolysis of Nitriles |
|
|
947 | (2) |
|
19.8 Enolate Nucleophiles: Aldol Additions |
|
|
949 | (3) |
|
|
|
952 | (2) |
|
19.10 Aldol Reactions Involving Ketones |
|
|
954 | (1) |
|
19.11 Crossed Aldol Reactions |
|
|
955 | (6) |
|
19.12 Intramolecular Aldol Reactions |
|
|
961 | (4) |
|
19.13 The Robinson Annulation |
|
|
965 | (1) |
|
19.14 Organic Synthesis: Aldol and Robinson Annulation Reactions in Synthesis |
|
|
966 | (3) |
|
The Organic Chemistry of Biomolecules |
|
|
|
19.15 Ring Opening and Ring Closing of Monosaccharides |
|
|
969 | (18) |
|
Chapter Summary and Key Terms |
|
|
973 | (1) |
|
|
|
974 | (3) |
|
|
|
977 | (10) |
|
20 Redox Reactions; Organometallic Reagents and Their Reactions |
|
|
987 | (38) |
|
20.1 Identifying Reactions as Redox Reactions |
|
|
988 | (4) |
|
20.2 A Deeper Look: Calculating Oxidation States |
|
|
992 | (2) |
|
20.3 Catalytic Hydrogenation: A Review of Alkene and Alkyne Reductions, Reductions of Other Functional Groups, and Selectivity |
|
|
994 | (3) |
|
20.4 Reactions That Reduce C=O to CH2: Wolff--Kishner, Clemmensen, and Raney--Nickel Reductions |
|
|
997 | (3) |
|
20.5 Oxidations of Alcohols and Aldehydes |
|
|
1000 | (5) |
|
20.6 Generating Organometallic Reagents: Grignard Reagents, Alkyllithium Reagents, and Lithium Dialkylcuprates |
|
|
1005 | (3) |
|
20.7 Useful Reactions That Form Carbon-Carbon Bonds: Coupling and Alkene Metathesis Reactions |
|
|
1008 | (17) |
|
Chapter Summary and Key Terms |
|
|
1014 | (1) |
|
|
|
1015 | (2) |
|
|
|
1017 | (8) |
|
21 Organic Synthesis 3 Intermediate Topics in Synthesis Design |
|
|
1025 | (26) |
|
21.1 Considerations When a Synthesis Calls for a New Carbon--Carbon Bond |
|
|
1026 | (9) |
|
21.2 Avoiding Synthetic Traps: Selective Reagents and Protecting Groups |
|
|
1035 | (16) |
|
Chapter Summary and Key Terms |
|
|
1045 | (1) |
|
|
|
1045 | (6) |
|
22 Nucleophilic Addition-Elimination Reactions 1 Reagents That Are Strongly Nucleophilic |
|
|
1051 | (48) |
|
22.1 An Introduction to Nucleophilic Addition-Elimination Reactions: Transesterification |
|
|
1052 | (5) |
|
22.2 Acyl Substitution Involving Other Carboxylic Acid Derivatives: The Thermodynamics of Acyl Substitution |
|
|
1057 | (4) |
|
22.3 Reaction of an Ester with Hydroxide (Saponification) and the Reverse Reaction |
|
|
1061 | (2) |
|
22.4 Carboxylic Acids from Amides; the Gabriel Synthesis of Primary Amines |
|
|
1063 | (6) |
|
|
|
1069 | (3) |
|
22.6 Hydride Reducing Agents: NaBH4 and LiAIH4 |
|
|
1072 | (9) |
|
22.7 A Deeper Look: DIBAH and LTBA as Specialized Reducing Agents |
|
|
1081 | (3) |
|
22.8 Organometallic Reagents |
|
|
1084 | (15) |
|
Chapter Summary and Key Terms |
|
|
1088 | (1) |
|
|
|
1089 | (2) |
|
|
|
1091 | (8) |
|
23 Nucleophilic Addition-Elimination Reactions 2 Reagents That Are Weakly Nucleophilic or Non-nucleophilic |
|
|
1099 | (57) |
|
23.1 The General Nucleophilic Addition--Elimination Mechanism Involving Weak Nucleophiles: Alcoholysis and Hydrolysis of Acid Chlorides |
|
|
1100 | (3) |
|
23.2 Relative Reactivities of Acid Derivatives: Rates of Hydrolysis |
|
|
1103 | (3) |
|
23.3 Aminolysis of Acid Derivatives |
|
|
1106 | (3) |
|
23.4 Synthesis of Acid Halides: Getting to the Top of the Stability Ladder |
|
|
1109 | (3) |
|
23.5 The Hell--Volhard--Zelinsky Reaction: Synthesizing α-Bromo Carboxylic Acids |
|
|
1112 | (2) |
|
23.6 Sulfonyl Chlorides: Synthesis of Mesylates, Tosylates, and Triflates |
|
|
1114 | (2) |
|
23.7 Base and Acid Catalysis in Nucleophilic Addition--Elimination Reactions |
|
|
1116 | (6) |
|
23.8 Baeyer--Villiger Oxidations |
|
|
1122 | (2) |
|
23.9 Claisen Condensation Reactions |
|
|
1124 | (10) |
|
23.10 Organic Synthesis: Decarboxylation, the Malonic Ester Synthesis, and the Acetoacetic Ester Synthesis |
|
|
1134 | (4) |
|
The Organic Chemistry of Biomolecules |
|
|
|
23.11 Determining the Amino Acid Sequence of a Protein |
|
|
1138 | (18) |
|
Chapter Summary and Key Terms |
|
|
1141 | (1) |
|
|
|
1142 | (2) |
|
|
|
1144 | (12) |
|
24 Aromatic Substitution 1 Electrophilic Aromatic Substitution on Benzene, and Useful Accompanying Reactions |
|
|
1156 | (41) |
|
24.1 The General Mechanism of Electrophilic Aromatic Substitution |
|
|
1157 | (3) |
|
|
|
1160 | (3) |
|
24.3 Friedel-Crafts Aikylation |
|
|
1163 | (3) |
|
24.4 Limitations of Friedel--Crafts Aikylation |
|
|
1166 | (4) |
|
24.5 Friedel--Crafts Acylation |
|
|
1170 | (3) |
|
|
|
1173 | (1) |
|
|
|
1174 | (2) |
|
24.8 Organic Synthesis: Considerations of Carbocation Rearrangements and the Synthesis of Primary Alkylbenzenes |
|
|
1176 | (1) |
|
24.9 Organic Synthesis: Common Reactions Used Along with Electrophilic Aromatic Substitution Reactions |
|
|
1177 | (20) |
|
Chapter Summary and Key Terms |
|
|
1186 | (1) |
|
|
|
1187 | (3) |
|
|
|
1190 | (7) |
|
25 Aromatic Substitution 2 Reactions of Substituted Benzenes and Other Rings |
|
|
1197 | (55) |
|
25.1 Regiochemistry of Electrophilic Aromatic Substitution: Defining Ortho/Para and Meta Directors |
|
|
1198 | (2) |
|
25.2 What Characterizes Ortho/Para and Meta Directors, and Why? |
|
|
1200 | (8) |
|
25.3 Activation and Deactivation of Benzene toward Electrophilic Aromatic Substitution |
|
|
1208 | (4) |
|
25.4 Impact of Substituent Effects on the Outcome of Electrophilic Aromatic Substitution Reactions |
|
|
1212 | (2) |
|
25.5 Impact of Reaction Conditions on Substituent Effects |
|
|
1214 | (2) |
|
25.6 Electrophilic Aromatic Substitution on Disubstituted Benzenes |
|
|
1216 | (6) |
|
25.7 Electrophilic Aromatic Substitution Involving Aromatic Rings other than Benzene |
|
|
1222 | (3) |
|
25.8 Azo Coupling and Azo Dyes |
|
|
1225 | (1) |
|
25.9 Nucleophilic Aromatic Substitution Mechanisms |
|
|
1226 | (6) |
|
25.10 Organic Synthesis: Considerations of Regiochemistry, and Attaching Groups in the Correct Order |
|
|
1232 | (1) |
|
25.11 Organic Synthesis: Interconverting Ortho/Para and Meta Directors |
|
|
1233 | (4) |
|
25.12 Organic Synthesis: Considerations of Protecting Groups |
|
|
1237 | (15) |
|
Chapter Summary and Key Terms |
|
|
1240 | (1) |
|
|
|
1241 | (1) |
|
|
|
1242 | (10) |
|
26 The Diels--Alder Reaction, Syn Dihydroxylation, and Oxidative Cleavage |
|
|
1252 | (52) |
|
26.1 Curved Arrow Notation and Examples of Diels--Alder Reactions |
|
|
1253 | (4) |
|
26.2 Conformation of the Diene in Diels--Alder Reactions |
|
|
1257 | (3) |
|
26.3 Substituent Effects on the Reaction Rate of Diels--Alder Reactions |
|
|
1260 | (2) |
|
26.4 Stereochemistry of Diels--Alder Reactions |
|
|
1262 | (6) |
|
26.5 Regiochemistry of Diels--Alder Reactions |
|
|
1268 | (3) |
|
26.6 A Deeper Look: The Reversibility of Diels--Alder Reactions; the Retro Diels--Alder Reaction |
|
|
1271 | (2) |
|
26.7 A Deeper Look: A Molecular Orbital Picture of the Diels--Alder Reaction |
|
|
1273 | (6) |
|
26.8 Syn Dihydroxylation of Alkenes and Alkynes with OsO4 or KMnO4 |
|
|
1279 | (2) |
|
26.9 Oxidative Cleavage of Alkenes and Alkynes |
|
|
1281 | (6) |
|
26.10 Organic Synthesis: The Diels--Alder Reaction in Synthesis |
|
|
1287 | (17) |
|
Chapter Summary and Key Terms |
|
|
1290 | (1) |
|
|
|
1291 | (2) |
|
|
|
1293 | (11) |
|
27 Reactions Involving Radicals |
|
|
1304 | (50) |
|
27.1 Homolysis: Curved Arrow Notation and Radical Initiators |
|
|
1305 | (3) |
|
27.2 Structure and Stability of Alkyl Radicals |
|
|
1308 | (6) |
|
27.3 Common Elementary Steps That Radicals Undergo |
|
|
1314 | (3) |
|
27.4 Radical Halogenation of Alkanes: Synthesis of Alkyl Halides |
|
|
1317 | (15) |
|
27.5 Radical Addition of HBr: Anti-Markovnikov Addition |
|
|
1332 | (3) |
|
27.6 Stereochemistry of Radical Halogenation and HBr Addition |
|
|
1335 | (2) |
|
27.7 Dissolving Metal Reductions: Hydrogenation of Alkenes and Alkynes |
|
|
1337 | (4) |
|
27.8 Organic Synthesis: Radical Reactions in Synthesis |
|
|
1341 | (13) |
|
Chapter Summary and Key Terms |
|
|
1344 | (1) |
|
|
|
1345 | (1) |
|
|
|
1346 | (8) |
|
|
|
1354 | (1) |
|
28.1 Radical Polymerization: Polystyrene as a Model |
|
|
1355 | (13) |
|
28.2 Anionic and Cationic Polymerization Reactions |
|
|
1368 | (3) |
|
28.3 Ziegler--Natta Catalysts and Coordination Polymerization |
|
|
1371 | (1) |
|
28.4 Ring-Opening Polymerization Reactions |
|
|
1372 | (2) |
|
28.5 Step-Growth Polymerization |
|
|
1374 | (6) |
|
28.6 Linear, Branched, and Network Polymers |
|
|
1380 | (2) |
|
28.7 Modification of Pendant Groups |
|
|
1382 | (3) |
|
|
|
1385 | (2) |
|
28.9 General Aspects of Polymer Structure |
|
|
1387 | (5) |
|
28.10 Properties of Polymers |
|
|
1392 | (6) |
|
28.11 Uses of Polymers: The Relationship between Structure and Function in Materials for Food Storage |
|
|
1398 | (2) |
|
28.12 Going Green with Polymers: Recycling, Biodegradable Polymers, and Renewable Sources |
|
|
1400 | (3) |
|
The Organic Chemistry of Biomolecules |
|
|
|
28.13 Biological Polymers |
|
|
1403 | (9) |
|
Chapter Summary and Key Terms |
|
|
1412 | (1) |
|
|
|
1413 | |
|
29 Biomolecules 1 An Overview of the Four Major Classes of Biomolecules |
|
|
|
PART 1 PROTEINS AND AMINO ACIDS |
|
|
|
29.1 Amino Acids as Building Blocks of Proteins |
|
|
|
29.2 Acid-Base Properties of Amino Acids: Ionization State as a Function of pH |
|
|
|
29.3 Electrophoresis and Isoelectric Focusing of Amino Acids |
|
|
|
29.4 Levels of Protein Structure: Primary, Secondary, Tertiary, and Quaternary Structures |
|
|
|
|
|
|
29.6 Synthesizing Peptides in the Laboratory |
|
|
|
PART 2 CARBOHYDRATES AND MONOSACCHARIDES |
|
|
|
29.7 Monosaccharides as Building Blocks of Carbohydrates |
|
|
|
29.8 Classification of Monosaccharides, and the D Family of Aldohexoses |
|
|
|
29.9 The Fischer Proof of the Structure of Glucose |
|
|
|
29.10 Ring Closing and Ring Opening of Sugars |
|
|
|
29.11 Glycosides, Glycosidic Linkages, and Reducing Sugars |
|
|
|
29.12 Polysaccharide Structure and Function |
|
|
|
PART 3 NUCLEIC ACIDS AND NUCLEOTIDES |
|
|
|
29.13 Nucleotides as Building Blocks of Nucleic Acids |
|
|
|
29.14 Complementarity among Nitrogenous Bases, and the DNA Double Helix |
|
|
|
|
|
|
29.15 Fats, Oils, and Fatty Acids |
|
|
|
29.16 Phospholipids and Cell Membranes |
|
|
|
29.17 Steroids, Terpenes, and Terpenoids |
|
|
|
|
|
|
|
|
|
Chapter Summary and Key Terms |
|
|
|
|
|
|
30 Biomolecules 2 Representative Biochemical Processes Involving Biomolecules |
|
|
|
|
|
|
30.2 Metabolism of Carbohydrates: Glycolysis and Gluconeogenesis |
|
|
|
30.3 Degradation and Synthesis of Fats, Oils, and Fatty Acids |
|
|
|
30.4 Biosynthesis of Cholesterol and Terpenes |
|
|
|
30.5 Storing and Accessing Genetic Information in DNA |
|
|
|
30.6 Cell Signaling: An Example Involving G Proteins |
|
|
|
Chapter Summary and Key Terms |
|
|
|
|
|
| Appendix A Values of pKa for Various Acids |
|
1 | (3) |
| Appendix B Characteristic Reactivities of Particular Compound Classes |
|
4 | (5) |
| Appendix C Reactions That Alter the Carbon Skeleton |
|
9 | (6) |
| Appendix D Synthesizing Particular Compound Classes via Functional Group Transformations |
|
15 | (18) |
| Appendix E Trivial Names or Common Names |
|
33 | |
| Glossary |
|
1 | (1) |
| Answers to Your Turns |
|
1 | (1) |
| Credits |
|
1 | (1) |
| Index |
|
1 | |
