vi CONTENTS

2.13 Bond energy and bond dissociation energy 28

2.14 3D-Structure of Csp3 compounds 30
2.15 Intramolecular forces 30
2.16 Polarity of bonds 31
2.17 Polarity of molecules 31
2.18 Structure and physical properties 34
2.19 Melting point 35
2.20 Intermolecular forces 36
2.21 Boiling point 38
2.22 Solubility 40

3 Symmetry of Organic Molecules (Molecular Dissymmetry) 43

3.1 Symmetry elements 43
3.2 Point groups 46
3.3 Determining the point group of organic molecules 47
3.4 Stereogenicity 48
3.5 Achiral stereogenicity 51
3.6 Stereoheterotopicity 52

4 Types of Reactions of Organic Compounds 55

4.1 Reaction mechanism 55
4.2 Electron delocalization 59
4.3 Formation of reaction intermediates 64
4.4 Transition state 89
4.5 Types of reagents 90
4.6 Types of organic reactions 90
4.7 Acids and bases 91
4.8 Hard and soft acids and bases (HSAB concept) 94
4.9 Thermodynamics of organic reactions 95
4.10 Kinetics of organic reactions 96
4.11 Thermodynamic and kinetic control of reactions 97
4.12 Effect of catalyst on the kinetics of a reaction 97
4.13 Linear free energy relationships (the Hammett equation) 98
4.14 Curved Hammett diagrams 101
4.15 Separation of polar, resonance, and steric effects of substituent
constants (s⫹ and s⫺) values 102
4.16 The Taft equation 103
4.17 Secondary bonding and role of solvent 103

5 Alkanes, Cycloalkanes and Aromatic Hydrocarbons 120

5AI. Introduction to Alkanes
5AI.1 Classification of hydrocarbons 120
5AI.2 Alkanes: structure of methane 120
5AI.3 Classification by structure: the family 121
5AI.4 Structure of ethane 122

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 CONTENTS vii

5AI.5 Free rotation about the carbon–carbon single bond.

Conformations. Torsional strain 123
5AI.6 Propane and the butanes 127
5AI.7 Conformations of n-butane. Van der Waals repulsion 129
5AI.8 Higher alkanes. The homologous series 131
5AI.9 Nomenclature 132
5AI.10 Alkyl groups 132
5AI.11 Common names of alkanes 134
5AI.12 IUPAC names of alkanes 134
5AI.13 Classes of carbon atoms and hydrogen atoms 136
5AI.14 Physical properties 136
5AI.15 Industrial source 138
5AI.16 Industrial source vs. laboratory preparation 140
5AI.17 Preparation 141
5AI.18 The Grignard reagent: an organometallic compound 143
5AI.19 Coupling of alkyl halides with organometallic compounds 145
5AI.20 Reactions 147
5AI.21 Halogenation 148
5AI.22 Mechanism of halogenation 150
5AI.23 Orientation of halogenation 151
5AI.24 Relative reactivities of alkanes toward halogenation 154
5AI.25 Ease of abstraction of hydrogen atoms. Energy of activation 155
5AI.26 Stability of free radicals 156
5AI.27 Ease of formation of free radicals 157
5AI.28 Transition state for halogenation 158
5AI.29 Orientation and reactivity 159
5AI.30 Reactivity and selectivity 160
5AI.31 Non-rearrangement of free radicals. Isotopic tracers 161
5AI.32 Combustion 163
5AI.33 The greenhouse effect 164
5AI.34 Pyrolysis: cracking 165
5AI.35 Determination of structure 166
5AII. Stereoisomerism
5AII.1 Stereoisomerism 169
5AII.2 Enantiomerism 169
5AII.3 Plane-polarized light 169
5AII.4 Polarimeter 170
5AII.5 Specific rotation 171
5AII.6 Optical activity: how does it arise? 172
5AII.7 Projection structures of stereoisomers 173
5AII.8 Properties of enantiomers 177
5AII.9 Racemic modification and resolution 179
5AII.10 Optical activity: a closer look 181
5AII.11 Assignment of configuration 182
5AII.12 Specification of configuration: R and S 183
5AII.13 Sequence rules 184
5AII.14 Diastereomers 186
5AII.15 Meso structures 188

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5AII.16 Specification of configuration: more than one chiral center 190

5AII.17 Conformational isomers 191
5AII.18 Reactions involving stereoisomers 193
5AII.19 Generation of a chiral center. Synthesis and optical activity 193
5AII.20 Reactions of chiral molecules. Bond-breaking 195
5AII.21 Reactions of chiral molecules. Relating configurations 196
5AII.22 Optical purity 199
5AII.23 Reactions of chiral molecules. Generation
of a second chiral center 199
5AII.24 Topicity of ligands (prochirality) 200
5BI. Cyclic Aliphatic Compounds (Carbocyclic Compounds)
5BI.1 Open-chain and cyclic compounds 206
5BI.2 Nomenclature 206
5BI.3 Industrial source 208
5BI.4 Preparation 209
5BI.5 Reactions 210
5BI.6 Reactions of small-ring compounds.
Cyclopropane and cyclobutane 211
5BI.7 Baeyer strain theory 212
5BI.8 Heats of combustion and relative stabilities
of the cycloalkanes 213
5BI.9 Orbital picture of angle strain 215
5BI.10 Factors affecting stability of conformations 216
5BI.11 Conformations of cycloalkanes 217
5BI.12 Equatorial and axial bonds in cyclohexane 222
5BI.13 Preparation of cyclopropane rings by ␲-insertion
reaction of carbenes 225
5BII. Stereoisomerism
5BII.1 Stereoisomerism of cycloalkanes and their derivatives:
configurational isomerism of cyclic compounds 228
5BII.2 Geometric isomerism of alkenes 230
5BII.3 Conformational analysis 233
5C. Aromatic Hydrocarbons and Aromaticity
5C.1 Aliphatic and aromatic compounds 243
5C.2 Structure of benzene 244
5C.3 Molecular formula. Isomer number. Kekulé structure 244
5C.4 Stability of the benzene ring. Reactions of benzene 246
5C.5 Stability of the benzene ring. Heats of hydrogenation and
combustion 247
5C.6 Carbon–carbon bond lengths in benzene 248
5C.7 Resonance structure of benzene 249
5C.8 Orbital picture of benzene 250
5C.9 Representation of the benzene ring 252
5C.10 Aromatic character. The Hückel 4n ⫹ 2 rule 253
5C.11 Nomenclature of benzene derivatives 257
5C.12 Polynuclear aromatic hydrocarbons. Naphthalene 259
5C.13 Electrophilic aromatic substitution 262
5C.14 Effect of substituent groups 265

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