Preface |
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xxiii | |
About the Author |
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xli | |
1 Introduction and Review |
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1 | (38) |
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1-1 The Origins of Organic Chemistry |
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1 | (2) |
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1-2 Principles of Atomic Structure |
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3 | (3) |
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1-3 Bond Formation: The Octet Rule |
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6 | (1) |
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7 | (1) |
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8 | (1) |
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Summary: Common Bonding Patterns (Uncharged) |
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9 | (1) |
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1-6 Electronegativity and Bond Polarity |
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9 | (2) |
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11 | (1) |
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12 | (1) |
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Summary: Common Bonding Patterns in Organic Compounds and Ions |
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13 | (1) |
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13 | (4) |
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17 | (3) |
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1-11 Molecular Formulas and Empirical Formulas |
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20 | (1) |
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1-12 Arrhenius Acids and Bases |
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21 | (1) |
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1-13 Bransted-Lowry Acids and Bases |
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22 | (7) |
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1-14 Lewis Acids and Bases |
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29 | (3) |
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32 | (2) |
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34 | (5) |
2 Structure and Properties of Organic Molecules |
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39 | (42) |
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2-1 Wave Properties of Electrons in Orbitals |
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39 | (2) |
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41 | (3) |
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44 | (1) |
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2-4 Hybridization and Molecular Shapes |
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45 | (4) |
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2-5 Drawing Three-Dimensional Molecules |
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49 | (1) |
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2-6 General Rules of Hybridization and Geometry |
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50 | (4) |
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54 | (2) |
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56 | (2) |
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2-9 Polarity of Bonds and Molecules |
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58 | (3) |
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2-10 Intermolecular Forces |
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61 | (4) |
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2-11 Polarity Effects on Solubilities |
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65 | (3) |
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68 | (3) |
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2-13 Organic Compounds Containing Oxygen |
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71 | (2) |
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2-14 Organic Compounds Containing Nitrogen |
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73 | (2) |
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75 | (2) |
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77 | (4) |
3 Structure and Stereochemistry of Alkanes |
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81 | (44) |
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3-1 Classification of Hydrocarbons (Review) |
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81 | (1) |
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3-2 Molecular Formulas of Alkanes |
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82 | (1) |
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3-3 Nomenclature of Alkanes |
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83 | (6) |
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Summary: Rules for Naming Alkanes |
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88 | (1) |
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3-4 Physical Properties of Alkanes |
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89 | (2) |
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3-5 Uses and Sources of Alkanes |
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91 | (2) |
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93 | (1) |
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3-7 Structure and Conformations of Alkanes |
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94 | (4) |
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3-8 Conformations of Butane |
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98 | (2) |
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3-9 Conformations of Higher Alkanes |
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100 | (1) |
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100 | (3) |
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3-11 cis-trans Isomerism in Cycloalkanes |
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103 | (1) |
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3-12 Stabilities of Cycloalkanes; Ring Strain |
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103 | (4) |
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3-13 Cyclohexane Conformations |
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107 | (4) |
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3-14 Conformations of Monosubstituted Cyclohexanes |
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111 | (3) |
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3-15 Conformations of Disubstituted Cyclohexanes |
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114 | (3) |
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117 | (2) |
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119 | (3) |
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122 | (3) |
4 The Study of Chemical Reactions |
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125 | (42) |
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125 | (1) |
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4-2 Chlorination of Methane |
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125 | (1) |
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4-3 The Free-Radical Chain Reaction |
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126 | (4) |
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Key Mechanism: Free-Radical Halogenation |
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128 | (2) |
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4-4 Equilibrium Constants and Free Energy |
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130 | (3) |
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133 | (1) |
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4-6 Bond-Dissociation Enthalpies |
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134 | (1) |
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4-7 Enthalpy Changes in Chlorination |
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135 | (2) |
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4-8 Kinetics and the Rate Equation |
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137 | (2) |
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4-9 Activation Energy and the Temperature Dependence of Rates |
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139 | (1) |
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140 | (2) |
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4-11 Rates of Multistep Reactions |
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142 | (1) |
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4-12 Temperature Dependence of Halogenation |
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143 | (1) |
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4-13 Selectivity in Halogenation |
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144 | (5) |
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4-14 The Hammond Postulate |
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149 | (4) |
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153 | (2) |
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4-16 Reactive Intermediates |
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155 | (5) |
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Summary: Reactive Intermediates |
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160 | (1) |
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160 | (3) |
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163 | (4) |
5 Stereochemistry |
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167 | (45) |
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167 | (1) |
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168 | (6) |
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5-3 (R) and (S) Nomenclature of Asymmetric Carbon Atoms |
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174 | (5) |
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179 | (5) |
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5-5 Biological Discrimination of Enantiomers |
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184 | (1) |
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185 | (1) |
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5-7 Enantiomeric Excess and Optical Purity |
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186 | (1) |
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5-8 Chirality of Conformationally Mobile Systems |
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187 | (2) |
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5-9 Chiral Compounds without Asymmetric Atoms |
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189 | (2) |
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191 | (5) |
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Summary: Fischer Projections and Their Use |
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196 | (1) |
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196 | (2) |
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Summary: Types of Isomers |
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197 | (1) |
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5-12 Stereochemistry of Molecules with Two or More Asymmetric Carbons |
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198 | (1) |
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199 | (2) |
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5-14 Absolute and Relative Configuration |
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201 | (2) |
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5-15 Physical Properties of Diastereomers |
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203 | (1) |
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5-16 Resolution of Enantiomers |
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204 | (3) |
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207 | (2) |
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209 | (3) |
6 Alkyl Halides: Nucleophilic Substitution and Elimination |
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212 | (67) |
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212 | (1) |
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6-2 Nomenclature of Alkyl Halides |
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213 | (2) |
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6-3 Common Uses of Alkyl Halides |
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215 | (2) |
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6-4 Structure of Alkyl Halides |
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217 | (1) |
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6-5 Physical Properties of Alkyl Halides |
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218 | (2) |
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6-6 Preparation of Alkyl Halides |
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220 | (5) |
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Summary: Methods for Preparing Alkyl Halides |
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223 | (2) |
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6-7 Reactions of Alkyl Halides: Substitution and Elimination |
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225 | (1) |
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6-8 Second-Order Nucleophilic Substitution: The SN2 Reaction |
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226 | (2) |
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Key Mechanism: The SN2 Reaction |
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227 | (1) |
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6-9 Generality of the SN2 Reaction |
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228 | (2) |
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Summary: SN2 Reactions of Alkyl Halides |
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228 | (2) |
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6-10 Factors Affecting SN2 Reactions: Strength of the Nucleophile |
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230 | (4) |
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Summary: Trends in Nucleophilicity |
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231 | (3) |
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6-11 Reactivity of the Substrate in SN2 Reactions |
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234 | (4) |
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6-12 Stereochemistry of the SN2 Reaction |
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238 | (2) |
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6-13 First-Order Nucleophilic Substitution: The SN1 Reaction |
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240 | (4) |
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Key Mechanism: The 5N1 Reaction |
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241 | (3) |
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6-14 Stereochemistry of the SN1 Reaction |
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244 | (2) |
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6-15 Rearrangements in SN I Reactions |
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246 | (3) |
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6-16 Comparison of SN1 and SN2 Reactions |
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249 | (3) |
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Summary: Nucleophilic Substitutions |
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251 | (1) |
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6-17 First-Order Elimination: The El Reaction |
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252 | (5) |
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Key Mechanism: The El Reaction |
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252 | (4) |
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Summary: Carbocation Reactions |
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256 | (1) |
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6-18 Positional Orientation of Elimination: Zaitsev's Rule |
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257 | (1) |
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6-19 Second-Order Elimination: The E2 Reaction |
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258 | (3) |
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Key Mechanism: The E2 Reaction |
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259 | (2) |
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6-20 Stereochemistry of the E2 Reaction |
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261 | (1) |
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6-21 Comparison of El and E2 Elimination Mechanisms |
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262 | (8) |
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Summary: Elimination Reactions |
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264 | (3) |
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Summary: Reactions of Alkyl Halides |
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267 | (3) |
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270 | (3) |
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273 | (6) |
7 Structure and Synthesis of Alkenes |
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279 | (42) |
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279 | (1) |
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7-2 The Orbital Description of the Alkene Double Bond |
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280 | (1) |
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7-3 Elements of Unsaturation |
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281 | (2) |
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7-4 Nomenclature of Alkenes |
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283 | (2) |
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7-5 Nomenclature of Cis-Trans Isomers |
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285 | (3) |
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Summary: Rules for Naming Alkenes |
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287 | (1) |
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7-6 Commercial Importance of Alkenes |
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288 | (2) |
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290 | (6) |
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7-8 Physical Properties of Alkenes |
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296 | (2) |
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7-9 Alkene Synthesis by Elimination of Alkyl Halides |
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298 | (8) |
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7-10 Alkene Synthesis by Dehydration of Alcohols |
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306 | (3) |
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Key Mechanism: Acid-Catalyzed Dehydration of an Alcohol |
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307 | (2) |
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7-11 Alkene Synthesis by High-Temperature Industrial Methods |
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309 | (7) |
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Summary: Methods for Synthesis of Alkenes |
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314 | (2) |
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316 | (2) |
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318 | (3) |
8 Reactions of Alkenes |
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321 | (61) |
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8-1 Reactivity of the Carbon-Carbon Double Bond |
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321 | (1) |
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8-2 Electrophilic Addition to Alkenes |
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322 | (2) |
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Key Mechanism: Electrophilic Addition to Alkenes |
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322 | (2) |
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8-3 Addition of Hydrogen Halides to Alkenes |
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324 | (6) |
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8-4 Addition of Water: Hydration of Alkenes |
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330 | (3) |
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8-5 Hydration by Oxymercuration-Demercuration |
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333 | (2) |
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8-6 Alkoxymercuration-Demercuration |
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335 | (1) |
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8-7 Hydroboration of Alkenes |
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336 | (6) |
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8-8 Addition of Halogens to Alkenes |
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342 | (3) |
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8-9 Formation of Halohydrins |
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345 | (3) |
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8-10 Catalytic Hydrogenation of Alkenes |
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348 | (2) |
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8-11 Addition of Carbenes to Alkenes |
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350 | (3) |
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8-12 Epoxidation of Alkenes |
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353 | (2) |
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8-13 Acid-Catalyzed Opening of Epoxides |
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355 | (3) |
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8-14 Syn Hydroxylation of Alkenes |
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358 | (2) |
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8-15 Oxidative Cleavage of Alkenes |
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360 | (3) |
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8-16 Polymerization of Alkenes |
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363 | (11) |
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Summary: Reactions of Alkenes |
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370 | (4) |
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374 | (2) |
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376 | (6) |
9 Alkynes |
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382 | (35) |
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382 | (1) |
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9-2 Nomenclature of Alkynes |
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383 | (1) |
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9-3 Physical Properties of Alkynes |
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384 | (1) |
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9-4 Commercial Importance of Alkynes |
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384 | (2) |
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9-5 Electronic Structure of Alkynes |
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386 | (1) |
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9-6 Acidity of Alkynes; Formation of Acetylide Ions |
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387 | (2) |
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9-7 Synthesis of Alkynes from Acetylides |
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389 | (4) |
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9-8 Synthesis of Alkynes by Elimination Reactions |
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393 | (3) |
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Summary: Syntheses of Alkynes |
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396 | (1) |
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9-9 Addition Reactions of Alkynes |
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396 | (10) |
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9-10 Oxidation of Alkynes |
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406 | (6) |
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Summary: Reactions of Alkynes |
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409 | (3) |
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412 | (1) |
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413 | (4) |
10 Structure and Synthesis of Alcohols |
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417 | (43) |
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417 | (1) |
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10-2 Structure and Classification of Alcohols |
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417 | (2) |
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10-3 Nomenclature of Alcohols and Phenols |
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419 | (4) |
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10-4 Physical Properties of Alcohols |
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423 | (2) |
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10-5 Commercially Important Alcohols |
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425 | (2) |
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10-6 Acidity of Alcohols and Phenols |
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427 | (3) |
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10-7 Synthesis of Alcohols: Introduction and Review |
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430 | (2) |
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Summary: Previous Alcohol Syntheses |
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430 | (2) |
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10-8 Organometallic Reagents for Alcohol Synthesis |
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432 | (3) |
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10-9 Addition of Organometallic Reagents to Carbonyl Compounds |
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435 | (8) |
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Key Mechanism: Grignard Reactions |
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435 | (7) |
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Summary: Grignard Reactions |
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442 | (1) |
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10-10 Side Reactions of Organometallic Reagents: Reduction of Alkyl Halides |
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443 | (2) |
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10-11 Reduction of the Carbonyl Group: Synthesis of 1° and 2° Alcohols |
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445 | (6) |
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Summary: Reactions of LiAlH4 and NaBH4 |
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448 | (1) |
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Summary: Alcohol Syntheses |
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449 | (2) |
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10-12 Thiols (Mercaptans) |
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451 | (3) |
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454 | (1) |
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455 | (5) |
11 Reactions of Alcohols |
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460 | (48) |
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11-1 Oxidation States of Alcohols and Related Functional Groups |
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460 | (2) |
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11-2 Oxidation of Alcohols |
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462 | (3) |
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11-3 Additional Methods for Oxidizing Alcohols |
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465 | (2) |
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11-4 Biological Oxidation of Alcohols |
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467 | (2) |
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11-5 Alcohols as Nucleophiles and Electrophiles; Formation of Tosylates |
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469 | (3) |
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Summary: SN2 Reactions of Tosylate Esters |
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471 | (1) |
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11-6 Reduction of Alcohols |
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472 | (1) |
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11-7 Reactions of Alcohols with Hydrohalic Acids |
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472 | (5) |
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11-8 Reactions of Alcohols with Phosphorus Halides |
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477 | (1) |
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11-9 Reactions of Alcohols with Thionyl Chloride |
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478 | (2) |
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11-10 Dehydration Reactions of Alcohols |
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480 | (8) |
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11-11 Unique Reactions of Diols |
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488 | (2) |
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11-12 Esterification of Alcohols |
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490 | (1) |
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11-13 Esters of Inorganic Acids |
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491 | (3) |
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11-14 Reactions of Alkoxides |
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494 | (8) |
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Key Mechanism: The Williamson Ether Synthesis |
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494 | (5) |
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Summary: Reactions of Alcohols |
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499 | (3) |
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502 | (1) |
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503 | (5) |
12 Infrared Spectroscopy and Mass Spectrometry |
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508 | (51) |
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508 | (1) |
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12-2 The Electromagnetic Spectrum |
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509 | (1) |
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510 | |
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12-4 Molecular Vibrations 51 |
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1 | (512) |
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12-5 1R-Active and IR-Inactive Vibrations |
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513 | (1) |
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12-6 Measurement of the IR Spectrum |
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514 | (3) |
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12-7 Infrared Spectroscopy of Hydrocarbons |
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517 | (5) |
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12-8 Characteristic Absorptions of Alcohols and Amines |
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522 | (1) |
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12-9 Characteristic Absorptions of Carbonyl Compounds |
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523 | (6) |
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12-10 Characteristic Absorptions of C-N Bonds |
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529 | (1) |
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12-11 Simplified Summary of IR Stretching Frequencies |
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530 | (2) |
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12-12 Reading and Interpreting IR Spectra (Solved Problems) |
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532 | (5) |
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12-13 Introduction to Mass Spectrometry |
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537 | (4) |
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12-14 Determination of the Molecular Formula by Mass Spectrometry |
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541 | (3) |
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12-15 Fragmentation Patterns in Mass Spectrometry |
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544 | (7) |
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Summary: Common Fragmentation Patterns |
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549 | (2) |
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551 | (1) |
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552 | (7) |
13 Nuclear Magnetic Resonance Spectroscopy |
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559 | (64) |
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559 | (1) |
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13-2 Theory of Nuclear Magnetic Resonance |
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559 | (3) |
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13-3 Magnetic Shielding by Electrons |
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562 | (2) |
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13-4 The NMR Spectrometer |
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564 | (1) |
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565 | (7) |
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13-6 The Number of Signals |
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572 | (1) |
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573 | (3) |
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576 | (9) |
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585 | (3) |
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13-10 Stereochemical Nonequivalence of Protons |
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588 | (3) |
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13-11 Time Dependence of NMR Spectroscopy |
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591 | (8) |
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Problem-Solving Strategy: Interpreting Proton NMR Spectra |
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594 | (5) |
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13-12 Carbon-13 NMR Spectroscopy |
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599 | (8) |
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13-13 Interpreting Carbon NMR Spectra |
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607 | (2) |
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13-14 Nuclear Magnetic Resonance Imaging |
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609 | (5) |
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Problem-Solving Strategy: Spectroscopy Problems |
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610 | (4) |
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614 | (2) |
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616 | (7) |
14 Ethers, Epoxides, and Sulfides |
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623 | (40) |
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623 | (1) |
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14-2 Physical Properties of Ethers |
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623 | (5) |
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14-3 Nomenclature of Ethers |
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628 | (3) |
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14-4 Spectroscopy of Ethers |
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631 | (2) |
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14-5 The Williamson Ether Synthesis |
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633 | (1) |
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14-6 Synthesis of Ethers by Alkoxymercuration-Demercuration |
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634 | (1) |
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14-7 Industrial Synthesis: Bimolecular Dehydration of Alcohols |
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635 | (1) |
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Summary: Syntheses of Ethers |
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636 | (1) |
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14-8 Cleavage of Ethers by HBr and HI |
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636 | (3) |
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14-9 Autoxidation of Ethers |
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639 | (1) |
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Summary: Reactions of Ethers |
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639 | (1) |
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14-10 Sulfides (Thioethers) |
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640 | (2) |
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14-11 Synthesis of Epoxides |
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642 | (3) |
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Summary: Epoxide Syntheses |
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645 | (1) |
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14-12 Acid-Catalyzed Ring Opening of Epoxides |
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645 | (4) |
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14-13 Base-Catalyzed Ring Opening of Epoxides |
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649 | (1) |
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14-14 Orientation of Epoxide Ring Opening |
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650 | (2) |
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14-15 Reactions of Epoxides with Grignard and Organolithium Reagents |
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652 | (1) |
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14-16 Epoxy Resins: The Advent of Modern Glues |
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653 | (3) |
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Summary: Reactions of Epoxides |
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655 | (1) |
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656 | (2) |
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658 | (5) |
15 Conjugated Systems, Orbital Symmetry, and Ultraviolet Spectroscopy |
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663 | (42) |
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663 | (1) |
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15-2 Stabilities of Dienes |
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663 | (2) |
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15-3 Molecular Orbital Picture of a Conjugated System |
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665 | (4) |
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669 | (1) |
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15-5 1,2- and 1,4-Addition to Conjugated Dienes |
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670 | (2) |
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15-6 Kinetic versus Thermodynamic Control in the Addition of HBr to 1,3-Butadiene |
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672 | (2) |
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674 | (2) |
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15-8 Molecular Orbitals of the Allylic System |
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676 | (2) |
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15-9 Electronic Configurations of the Ally! Radical, Cation, and Anion |
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678 | (1) |
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15-10 SN2 Displacement Reactions of Allylic Halides and Tosylates |
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679 | (1) |
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15-11 The Diels-Alder Reaction |
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680 | (9) |
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Key Mechanism: The Diels-Alder Reaction |
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680 | (9) |
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15-12 The Diels-Alder as an Example of a Pericyclic Reaction |
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689 | (3) |
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15-13 Ultraviolet Absorption Spectroscopy |
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692 | (7) |
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699 | (2) |
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701 | (4) |
16 Aromatic Compounds |
|
705 | (44) |
|
16-1 Introduction: The Discovery of Benzene |
|
|
705 | (1) |
|
16-2 The Structure and Properties of Benzene |
|
|
705 | (4) |
|
16-3 The Molecular Orbitals of Benzene |
|
|
709 | (3) |
|
16-4 The Molecular Orbital Picture of Cyclobutadiene |
|
|
712 | (2) |
|
16-5 Aromatic, Antiaromatic, and Nonaromatic Compounds |
|
|
714 | (1) |
|
|
714 | (2) |
|
16-7 Molecular Orbital Derivation of Hiickel's Rule |
|
|
716 | (1) |
|
|
717 | (6) |
|
16-9 Heterocyclic Aromatic Compounds |
|
|
723 | (4) |
|
16-10 Polynuclear Aromatic Hydrocarbons |
|
|
727 | (2) |
|
16-11 Aromatic Allotropes of Carbon |
|
|
729 | (2) |
|
16-12 Fused Heterocyclic Compounds |
|
|
731 | (1) |
|
16-13 Nomenclature of Benzene Derivatives |
|
|
732 | (2) |
|
16-14 Physical Properties of Benzene and Its Derivatives |
|
|
734 | (1) |
|
16-15 Spectroscopy of Aromatic Compounds |
|
|
735 | (3) |
|
|
738 | (2) |
|
|
740 | (9) |
17 Reactions of Aromatic Compounds |
|
749 | (56) |
|
17-1 Electrophilic Aromatic Substitution |
|
|
749 | (2) |
|
Key Mechanism: Electrophilic Aromatic Substitution |
|
|
750 | (1) |
|
17-2 Halogenation of Benzene |
|
|
751 | (2) |
|
17-3 Nitration of Benzene |
|
|
753 | (2) |
|
17-4 Sulfonation of Benzene |
|
|
755 | (2) |
|
17-5 Nitration of Toluene: The Effect of Alkyl Substitution |
|
|
757 | (2) |
|
17-6 Activating, Ortho, Para-Directing Substituents |
|
|
759 | (4) |
|
Summary: Activating, Ortho, Para-Directors |
|
|
762 | (1) |
|
17-7 Deactivating, Meta-Directing Substituents |
|
|
763 | (3) |
|
Summary: Deactivating, Meta-Directors |
|
|
766 | (1) |
|
17-8 Halogen Substituents: Deactivating, but Ortho, Para-Directing |
|
|
766 | (2) |
|
Summary: Directing Effects of Substituents |
|
|
768 | (1) |
|
17-9 Effects of Multiple Substituents on Electrophilic Aromatic Substitution |
|
|
768 | (3) |
|
17-10 The Friedel-Crafts Alkylation |
|
|
771 | (4) |
|
17-11 The Friedel-Crafts Acylation |
|
|
775 | (5) |
|
Summary: Comparison of Friedel-Crafts Alkylation and Acylation |
|
|
778 | (2) |
|
17-12 Nucleophilic Aromatic Substitution |
|
|
780 | (5) |
|
17-13 Addition Reactions of Benzene Derivatives |
|
|
785 | (2) |
|
17-14 Side-Chain Reactions of Benzene Derivatives |
|
|
787 | (4) |
|
17-15 Reactions of Phenols |
|
|
791 | (6) |
|
Summary: Reactions of Aromatic Compounds |
|
|
794 | (3) |
|
|
797 | (3) |
|
|
800 | (5) |
18 Ketones and Aldehydes |
|
805 | (65) |
|
|
805 | (1) |
|
18-2 Structure of the Carbonyl Group |
|
|
806 | (1) |
|
18-3 Nomenclature of Ketones and Aldehydes |
|
|
806 | (3) |
|
18-4 Physical Properties of Ketones and Aldehydes |
|
|
809 | (2) |
|
18-5 Spectroscopy of Ketones and Aldehydes |
|
|
811 | (7) |
|
18-6 Industrial Importance of Ketones and Aldehydes |
|
|
818 | (1) |
|
18-7 Review of Syntheses of Ketones and Aldehydes |
|
|
818 | (4) |
|
18-8 Synthesis of Ketones and Aldehydes Using 1,3-Dithianes |
|
|
822 | (1) |
|
18-9 Synthesis of Ketones from Carboxylic Acids |
|
|
823 | (1) |
|
18-10 Synthesis of Ketones from Nitriles |
|
|
824 | (1) |
|
18-11 Synthesis of Aldehydes and Ketones from Acid Chlorides |
|
|
825 | (4) |
|
Summary: Syntheses of Ketones and Aldehydes |
|
|
826 | (3) |
|
18-12 Reactions of Ketones and Aldehydes: Nucleophilic Addition |
|
|
829 | (3) |
|
Key Mechanism: Nucleophilic Additions to Carbonyl Groups |
|
|
831 | (1) |
|
18-13 The Wittig Reaction |
|
|
832 | (4) |
|
18-14 Hydration of Ketones and Aldehydes |
|
|
836 | (2) |
|
18-15 Formation of Cyanohydrins |
|
|
838 | (2) |
|
18-16 Formation of Imines |
|
|
840 | (3) |
|
Key Mechanism: Formation of Imines |
|
|
840 | (3) |
|
18-17 Condensations with Hydroxylamine and Hydrazines |
|
|
843 | (2) |
|
Summary: Condensations of Amines with Ketones and Aldehydes |
|
|
844 | (1) |
|
18-18 Formation of Acetals |
|
|
845 | (5) |
|
Key Mechanism: Formation of Acetals |
|
|
846 | (2) |
|
Problem-Solving Strategy: Proposing Reaction Mechanisms |
|
|
848 | (2) |
|
18-19 Use of Acetals as Protecting Groups |
|
|
850 | (2) |
|
18-20 Oxidation of Aldehydes |
|
|
852 | (1) |
|
18-21 Reductions of Ketones and Aldehydes |
|
|
853 | (5) |
|
Summary: Reactions of Ketones and Aldehydes |
|
|
855 | (3) |
|
|
858 | (3) |
|
|
861 | (9) |
19 Amines |
|
870 | (65) |
|
|
870 | (1) |
|
19-2 Nomenclature of Amines |
|
|
871 | (2) |
|
|
873 | (2) |
|
19-4 Physical Properties of Amines |
|
|
875 | (2) |
|
|
877 | (1) |
|
19-6 Effects on Amine Basicity |
|
|
878 | (2) |
|
|
880 | (2) |
|
19-8 Amine Salts as Phase-Transfer Catalysts |
|
|
882 | (2) |
|
19-9 Spectroscopy of Amines |
|
|
884 | (4) |
|
19-10 Reactions of Amines with Ketones and Aldehydes (Review) |
|
|
888 | (1) |
|
19-11 Aromatic Substitution of Arylamines and Pyridine (Review) |
|
|
888 | (4) |
|
19-12 Alkylation of Amines by Alkyl Halides |
|
|
892 | (1) |
|
19-13 Acylation of Amines by Acid Chlorides |
|
|
893 | (2) |
|
19-14 Formation of Sulfonamides |
|
|
895 | (2) |
|
19-15 Amines as Leaving Groups: The Hofmann Elimination |
|
|
897 | (3) |
|
19-16 Oxidation of Amines: The Cope Elimination |
|
|
900 | (2) |
|
19-17 Reactions of Amines with Nitrous Acid |
|
|
902 | (2) |
|
19-18 Reactions of Arenediazonium Salts |
|
|
904 | (7) |
|
Summary: Reactions of Amines |
|
|
908 | (3) |
|
19-19 Synthesis of Amines by Reductive Amination |
|
|
911 | (2) |
|
19-20 Synthesis of Amines by Acylation-Reduction |
|
|
913 | (2) |
|
19-21 Syntheses Limited to Primary Amines |
|
|
915 | (8) |
|
Summary: Synthesis of Amines |
|
|
921 | (2) |
|
|
923 | (3) |
|
|
926 | (9) |
20 Carboxylic Acids |
|
935 | (43) |
|
|
935 | (1) |
|
20-2 Nomenclature of Carboxylic Acids |
|
|
935 | (4) |
|
20-3 Structure and Physical Properties of Carboxylic Acids |
|
|
939 | (1) |
|
20-4 Acidity of Carboxylic Acids |
|
|
940 | (4) |
|
20-5 Salts of Carboxylic Acids |
|
|
944 | (3) |
|
20-6 Commercial Sources of Carboxylic Acids |
|
|
947 | (1) |
|
20-7 Spectroscopy of Carboxylic Acids |
|
|
948 | (4) |
|
20-8 Synthesis of Carboxylic Acids |
|
|
952 | (5) |
|
Summary: Syntheses of Carboxylic Acids |
|
|
955 | (2) |
|
20-9 Reactions of Carboxylic Acids and Derivatives; Nucleophilic Acyl Substitution |
|
|
957 | (1) |
|
20-10 Condensation of Acids with Alcohols: The Fischer Esterification |
|
|
958 | (4) |
|
Key Mechanism: Fischer Esterification |
|
|
959 | (3) |
|
20-11 Esterification Using Diazomethane |
|
|
962 | (1) |
|
20-12 Condensation of Acids with Amines: Direct Synthesis of Amides |
|
|
963 | (1) |
|
20-13 Reduction of Carboxylic Acids |
|
|
963 | (2) |
|
20-14 Alkylation of Carboxylic Acids to Form Ketones |
|
|
965 | (1) |
|
20-15 Synthesis and Use of Acid Chlorides |
|
|
966 | (4) |
|
Summary: Reactions of Carboxylic Acids |
|
|
968 | (2) |
|
|
970 | (1) |
|
|
971 | (7) |
21 Carboxylic Acid Derivatives |
|
978 | (63) |
|
|
978 | (1) |
|
21-2 Structure and Nomenclature of Acid Derivatives |
|
|
979 | (6) |
|
21-3 Physical Properties of Carboxylic Acid Derivatives |
|
|
985 | (3) |
|
21-4 Spectroscopy of Carboxylic Acid Derivatives |
|
|
988 | (6) |
|
21-5 Interconversion of Acid Derivatives by Nucleophilic Acyl Substitution |
|
|
994 | (9) |
|
Key Mechanism: Addition-Elimination Mechanism of Nucleophilic Acyl Substitution |
|
|
995 | (8) |
|
|
1003 | (3) |
|
21-7 Hydrolysis of Carboxylic Acid Derivatives |
|
|
1006 | (5) |
|
21-8 Reduction of Acid Derivatives |
|
|
1011 | (2) |
|
21-9 Reactions of Acid Derivatives with Organometallic Reagents |
|
|
1013 | (1) |
|
21-10 Summary of the Chemistry of Acid Chlorides |
|
|
1014 | (2) |
|
21-11 Summary of the Chemistry of Anhydrides |
|
|
1016 | (3) |
|
21-12 Summary of the Chemistry of Esters |
|
|
1019 | (3) |
|
21-13 Summary of the Chemistry of Amides |
|
|
1022 | (3) |
|
21-14 Summary of the Chemistry of Nitriles |
|
|
1025 | (1) |
|
|
1026 | (2) |
|
21-16 Esters and Amides of Carbonic Acid |
|
|
1028 | (2) |
|
|
1030 | (2) |
|
|
1032 | (9) |
22 Condensations and Alpha Substitutions of Carbonyl Compounds |
|
1041 | (56) |
|
|
1041 | (1) |
|
22-2 Enols and Enolate Ions |
|
|
1042 | (4) |
|
22-3 Alpha Halogenation of Ketones |
|
|
1046 | (5) |
|
22-4 a Bromination of Acids: The HVZ Reaction |
|
|
1051 | (1) |
|
22-5 Alkylation of Enolate Ions |
|
|
1052 | (1) |
|
22-6 Formation and Alkylation of Enamines |
|
|
1053 | (3) |
|
22-7 The Aldol Condensation of Ketones and Aldehydes |
|
|
1056 | (4) |
|
Key Mechanism: Base-Catalyzed Aldol Condensation |
|
|
1056 | (4) |
|
22-8 Dehydration of Aldol Products |
|
|
1060 | (1) |
|
Key Mechanism: Base-Catalyzed Dehydration of an Aldol |
|
|
1060 | (1) |
|
22-9 Crossed Aldol Condensations |
|
|
1061 | (3) |
|
Problem-Solving Strategy: Proposing Reaction Mechanisms |
|
|
1062 | (2) |
|
|
1064 | (1) |
|
22-11 Planning Syntheses Using Aldol Condensations |
|
|
1065 | (2) |
|
22-12 The Claisen Ester Condensation |
|
|
1067 | (3) |
|
Key Mechanism: The Claisen Ester Condensation |
|
|
1067 | (3) |
|
22-13 The Dieckmann Condensation: A Claisen Cyclization |
|
|
1070 | (1) |
|
22-14 Crossed Claisen Condensations |
|
|
1071 | (3) |
|
22-15 Syntheses Using /3-Dicarbonyl Compounds |
|
|
1074 | (2) |
|
22-16 The Malonic Ester Synthesis |
|
|
1076 | (3) |
|
22-17 The Acetoacetic Ester Synthesis |
|
|
1079 | (2) |
|
22-18 Conjugate Additions: The Michael Reaction |
|
|
1081 | (4) |
|
22-19 The Robinson Annulation |
|
|
1085 | (3) |
|
Problem-Solving Strategy: Proposing Reaction |
|
|
|
|
1086 | (2) |
|
Summary: Enolate Additions and Condensations |
|
|
1088 | (2) |
|
|
1090 | (2) |
|
|
1092 | (5) |
23 Carbohydrates and Nucleic Acids |
|
1097 | (56) |
|
|
1097 | (1) |
|
23-2 Classification of Carbohydrates |
|
|
1098 | (1) |
|
|
1099 | (3) |
|
23-4 Erythro and Threo Diastereomers |
|
|
1102 | (1) |
|
|
1103 | (1) |
|
23-6 Cyclic Structures of Monosaccharides |
|
|
1104 | (4) |
|
23-7 Anomers of Monosaccharides; Mutarotation |
|
|
1108 | (2) |
|
23-8 Reactions of Monosaccharides: Side Reactions in Base |
|
|
1110 | (2) |
|
23-9 Reduction of Monosaccharides |
|
|
1112 | (1) |
|
23-10 Oxidation of Monosaccharides; Reducing Sugars |
|
|
1113 | (2) |
|
23-11 Nonreducing Sugars: Formation of Glycosides |
|
|
1115 | (2) |
|
23-12 Ether and Ester Formation |
|
|
1117 | (2) |
|
23-13 Reactions with Phenylhydrazine: Osazone Formation |
|
|
1119 | (1) |
|
23-14 Chain Shortening: The Ruff Degradation |
|
|
1120 | (1) |
|
23-15 Chain Lengthening: The Kiliani-Fischer Synthesis |
|
|
1121 | (3) |
|
Summary: Reactions of Sugars |
|
|
1122 | (2) |
|
23-16 Fischer's Proof of the Configuration of Glucose |
|
|
1124 | (3) |
|
23-17 Determination of Ring Size; Periodic Acid Cleavage of Sugars |
|
|
1127 | (2) |
|
|
1129 | (5) |
|
|
1134 | (3) |
|
23-20 Nucleic Acids: Introduction |
|
|
1137 | (2) |
|
23-21 Ribonucleosides and Ribonucleotides |
|
|
1139 | (2) |
|
23-22 The Structure of Ribonucleic Acid |
|
|
1141 | (1) |
|
23-23 Deoxyribose and the Structure of Deoxyribonucleic Acid |
|
|
1141 | (4) |
|
23-24 Additional Functions of Nucleotides |
|
|
1145 | (2) |
|
|
1147 | (2) |
|
|
1149 | (4) |
24 Amino Acids, Peptides, and Proteins |
|
1153 | (47) |
|
|
1153 | (1) |
|
24-2 Structure and Stereochemistry of the a-Amino Acids |
|
|
1154 | (4) |
|
24-3 Acid-Base Properties of Amino Acids |
|
|
1158 | (2) |
|
24-4 Isoelectric Points and Electrophoresis |
|
|
1160 | (1) |
|
24-5 Synthesis of Amino Acids |
|
|
1161 | (6) |
|
Summary: Syntheses of Amino Acids |
|
|
1166 | (1) |
|
24-6 Resolution of Amino Acids |
|
|
1167 | (1) |
|
24-7 Reactions of Amino Acids |
|
|
1167 | (3) |
|
Summary: Reactions of Amino Acids |
|
|
1170 | (1) |
|
24-8 Structure and Nomenclature of Peptides and Proteins |
|
|
1170 | (4) |
|
24-9 Peptide Structure Determination |
|
|
1174 | (6) |
|
24-10 Solution-Phase Peptide Synthesis |
|
|
1180 | (3) |
|
24-11 Solid-Phase Peptide Synthesis |
|
|
1183 | (5) |
|
24-12 Classification of Proteins |
|
|
1188 | (1) |
|
24-13 Levels of Protein Structure |
|
|
1189 | (2) |
|
24-14 Protein Denaturation |
|
|
1191 | (2) |
|
|
1193 | (3) |
|
|
1196 | (4) |
25 Lipids |
|
1200 | (22) |
|
|
1200 | (1) |
|
|
1200 | (1) |
|
|
1201 | (3) |
|
25-4 Saponification of Fats and Oils; Soaps and Detergents |
|
|
1204 | (4) |
|
|
1208 | (1) |
|
|
1209 | (3) |
|
|
1212 | (1) |
|
|
1213 | (4) |
|
|
1217 | (1) |
|
|
1218 | (4) |
26 Synthetic Polymers |
|
1222 | (21) |
|
|
1222 | (1) |
|
|
1223 | (6) |
|
26-3 Stereochemistry of Polymers |
|
|
1229 | (1) |
|
26-4 Stereochemical Control of Polymerization; Ziegler-Natta Catalysts |
|
|
1230 | (1) |
|
26-5 Natural and Synthetic Rubbers |
|
|
1230 | (2) |
|
26-6 Copolymers of Two or More Monomers |
|
|
1232 | (1) |
|
26-7 Condensation Polymers |
|
|
1232 | (4) |
|
26-8 Polymer Structure and Properties |
|
|
1236 | (2) |
|
|
1238 | (2) |
|
|
1240 | (3) |
Appendices |
|
1243 | |
|
1A NMR Absorption Positions of Protons in Various Structural Environments |
|
|
1244 | (2) |
|
1B Spin-Spin Coupling Constants |
|
|
1246 | (1) |
|
1C 13C Chemical Shifts in Organic Compounds |
|
|
1247 | (1) |
|
2A Characteristic Infrared Group Frequencies |
|
|
1248 | (3) |
|
2B IR: Characteristic Infrared Absorptions of Functional Groups |
|
|
1251 | (2) |
|
3 UV: The Woodward-Fieser Rules for Predicting UV-Visible Spectra |
|
|
1253 | (4) |
|
4A Methods and Suggestions for Proposing Mechanisms |
|
|
1257 | (3) |
|
4B Suggestions for Developing Multistep Syntheses |
|
|
1260 | (1) |
|
5 pKa Values for Representative Compounds |
|
|
1261 | |
Answers to Selected Problems |
|
A1 | |
Photo Credits |
|
PC1 | |
Index |
|
l1 | |