WHAT IS ORGANIC CHEMISTRY?
Part I: Fundamentals 1 Introduction|3 11 What Is Organic Chemistry?|3 12 Bonding|3 121 Ionic Bonds|3 122 Covalent Bonds|4 123 Molecular Orbitals|5 124 Hybridization|7 13 Three-Dimensional Properties of Carbon|8 14 Polar Covalent Bonds|10 15 Bonding Between Carbon Atoms|10 16 Summary|12 17 Problems|12 2 The Simplest Organic Molecules – The Hydrocarbons|14 21 Definitions|14 22 Positional (or Constitutional) Isomers|14 23 Writing Formulae|15 24 Index of Hydrogen Deficiency|16 25 Naming Organic Compounds|17 26 Functional Group Concept|19 27 Additional Definitions|21 28 Problems|21 3 The Shapes of Organic Molecules – Stereochemistry 1|24 31 Introduction|24 32 The Structure of Some Simple Alkanes|24 33 Newman Projections and Conformations|25 34 Stabilities of Conformational Isomers|27 35 Stereoisomers|30 36 Stereochemical Designations – The Cahn–Ingold–Prelog System|32 37 The Sequence Rules|33 38 Alicyclic Compounds|35 39 Cyclohexane|37 310 Monosubstituted Cyclohexanes|39 311 Disubstituted Cyclohexanes|40 312 Problems|42 4 Reactions – Basic Principles (or Where, Why, What, How Fast, and How Far)|45 41 Introduction|45 42 Acids, Bases, and Moving Electrons|45 43 Reversibility|47 44 Chemical Thermodynamics (How Large is Keq)|47 45 Kinetics (How Fast)|48 46 Kinetic Versus Thermodynamic Control|50 47 Molecularity of Reactions|51 48 Nucleophiles and Electrophiles|52 49 Inductive and Steric Effects|53 410 Resonance Effects|54 411 How Important is Resonance?|57 412 Reaction Types|58 413 Summing Up|59 414 Problems|59 5 Reactions of Alkanes, Alkenes, and Alkynes|61 51 Introduction|61 52 Reactions of Alkanes|61 521 Oxidation|61 522 Halogenation|62 53 Electrophilic Addition to Alkenes: Our First Mechanism|62 54 Carbocation Stabilities (Markownikov’s Rule)|64 55 Catalysis|66 56 Stereochemistry|67 57 Functional Group Characterization|68 58 Solvent Effects (Regiochemistry)|69 59 Resonance Effects on Electrophilic Addition Reactions|71 510 Other Reactions of Alkenes|73 5101 Hydroboration|73 5102 Hydrogenation|74 5103 Oxidation|75 511 Reactions of Alkynes|76 5111 Hydrogenation|76 5112 Hydration|77 512 Summary|77 513 Problems|78 6 More Stereochemistry and Another Reaction Type – Nucleophilic Substitution|82 61 Introduction|82 62 Optical Isomerism (or Chemistry with Mirrors)|82 63 Polarimetry|84 64 Nomenclature – The R and S System|85 65 Fischer Projections|87 66 Assigning Configurations from Fisher Projections|91 67 Compounds With More Than One Chiral Center|91 68 Meso Forms|93 69 Resolution and Racemization|95 610 Why Is All This Stereochemistry Important? (Subtitle:What Am I Doing Here?)|96 611 Nucleophilic Substitution|97 612 The Carbocation Route – SN1 Reactions|97 613 The Concerted Route – SN2 Reactions|98 614 Stereochemistry Again|99 615 Which Mechanism Operates? – The Basic Factors|102 6151 The Carbon Center|102 6152 The Leaving Group|103 6153 The Nucleophile|104 6154 Solvent Effects|105 616 Putting It All Together|106 617 The Scope of Nucleophilic Substitution|106 618 Reversibility and Catalysis|107 619 Problems|109 7 Alcohols and Ethers, Amines, and Alkyl Halides Introduction to Carbonyl Compounds (Aldehydes, Ketones)|116 71 Introduction|116 72 Alcohols and Ethers – Chemical and Physical Properties|116 73 Preparation of Alcohols and Ethers|117 74 Reactions of Alcohols|118 75 Reactions of Ethers|119 76 Preparations of Alkyl Halides|120 77 Amines|121 78 Introduction to Carbonyl Groups|122 79 The Carbonyl Group – Nucleophilic Addition|122 710 Aldehydes and Ketones – Structure and Physical Properties|124 711 Preparations of Aldehydes and Ketones|125 712 Reactions of Aldehydes and Ketones|125 7121 General Considerations|125 7122 Catalysis|126 7123 Ketals and Acetals|128 7124 Protecting Groups|129 7125 Other Nucleophilic Addition Reactions|131 713 The Grignard Reaction – Introduction|133 7131 The Grignard Reagent|133 7132 The Grignard Reaction|133 7133 Acetylide Ions as Grignard Reagents|136 714 Reductions with Metal Hydrides|136 715 Other Reactions of Aldehydes and Ketones|137 7151 Oxidation|137 7152 The Iodoform Test|138 716 Introduction to Multistage Syntheses|138 717 Problems|139 8 More Carbonyl Chemistry – Acids and Their Derivatives|148 81 Introduction|148 82 Carboxylic Acids, Esters, Chlorides, Anhydrides, Amides (and Nitriles)|148 83 Physical and Chemical Properties of Carboxylic Acids|148 84 Preparations of Carboxylic Acids|150 85 Reactions of Carboxylic Acids – Esterification|150 86 Reactions of Esters|152 861 Detergents|154 87 Acyl Halides|156 88 Anhydrides|157 89 Amides|158 810 Nitriles|158 811 Other Reactions of Acids and Their Derivatives|159 8111 Grignard Reactions|159 8112 Reduction|160 812 Problems|160 9 Aromatic Compounds – Benzene and Its Derivatives Resonance as a Force Majeure|165 91 Introduction|165 92 Aromatic Molecules, Aromaticity, and Hückel’s Rule|165 93 Benzene – The Prototype of Aromatic Molecules|167 94 Reactions of Aromatic Molecules|168 941 General Considerations|168 942 Nitration|169 943 Halogenation|169 944 Acylation|170 945 Alkylation|170 95 Reversibility|171 96 Reactions of Substituted Benzenes|171 961 General Considerations|171 962 Reactivities|173 963 Orientations|174 964 Summary|176 965 Which Is It – Ortho or Para?|176 97 Reactions of Disubstituted Compounds|177 98 Some Special Functional Group Transformations|177 99 Control of Reactivity|179 910 Synthetic Problems|180 911 The Benzylic Position|182 912 Final Words On Reactions|183 913 Phenols and Anilines|184 9131 Acidity of Phenol|184 9132 Diazonium Salts|184 914 Problems|186 10 Organic Nitrogen Compounds – Amines and Amides|191 101 Introduction|191 102 Amines|191 1021 Nomenclature, Physical and Chemical Properties|191 1022 Preparation of Amines|193 1023 Reactions of Amines (Other Than alkylation)|195 1024 Heterocycles|196 1025 Separations of Organic Mixtures|197 103 Amides|198 1031 Amides – Nomenclature, Physical, and Chemical Properties|198 1032 Preparation of Amides|199 1033 Reactions of Amides|199 104 Problems|201 11 Introduction to Spectroscopy|205 111 Introduction|205 112 First Things First|205 113 Infrared (IR) Spectroscopy|206 1131 Introduction and General Principles|206 1132 IR Correlations|207 114 The Appearance of an IR Spectrum|208 115 How to Use IR data|209 116 Nuclear Magnetic Resonance|209 117 The Scale|211 118 The Chemical Shift|211 119 The Integral|213 1110 13C NMR Spectra|214 1111 Spin–Spin Coupling|216 1112 Shoolery’s Rules|219 1113 Putting It All Together|219 1114 Problems|225 12 Elimination Reactions|237 121 Introduction|237 122 Possible Mechanisms – Background and Review|237 123 E1 Mechanism – The Carbocation Route|238 124 The E2 Mechanism – The Concerted Route|240 1241 Prototypical E2 Elimination Reactions|241 125 Regiochemistry and Stereochemistry of Eliminations|241 1251 E1 Eliminations|242 1252 E2 Eliminations|243 126 Stereochemical Effects in E2 Eliminations|245 1261 Consequences in Cyclic Systems|246 127 E1 Versus E2 Eliminations|249 1271 Leaving Group|249 1272 Base|249 1273 Substrate Structure|249 1274 Solvent|250 128 Elimination Versus Substitution (E2 vs SN2)|250 1281 Nature of Base|250 1282 Nature of Substrate|251 129 The E1cB Mechanism|252 1210 Problems|253 13 Introduction to the Molecules of Nature|256 131 Introduction|256 132 Amino Acids, Peptides and Proteins|258 133 Lipids (Fats) and Steroids|260 1331 Lipids (aka Fats)|260 1332 Steroids|261 134 Vitamins|262 135 Alkaloids|263 136 Nucleic Acids (and Nucleosides)|264 137 Summary|265