Contents vii 6.21 Preparation 97 622 Reactions 98 6.3 Alkynes 631 Preparation 110 6.3.2 Reactions 110 Worked example 113 Problems 7 Benzenes 117 7.1 Structure 117 7.2 Reactions 119 721 Halogenation 119 722 Nitration 120 7.23 Sulfonation 120 7.24 Alkylation:The Friedel-Crafts alkylation 7.25 Acylation:The Friedel-Crafts acylation 122 7.3 Reactivity of substituted benzenes 123 7.3.1 Reactivity of benzene rings:Activating and deactivating substituents 7.3.2 Orientation of reactions 125 14 Nucleophilic aromatic substitution (the SxAr mechanism) 127 The formation of benzyne Transformation of side chains 129 Reduction of the benzene ring 132 7.8 The synthesis of substituted benzenes 132 79 Electrophilic substitution of naphthalene 135 7.10 Electrophilic substitution of pyridine 135 7.11 Electrophilic substitution of 136 Worked example 136 Problems 137 8 Carbonyl compounds:aldehydes and ketones 139 81 Structure 139 8. Reactivity 140 8.3 Nucleophilic addition reactions 142 8.3.1 Relative reactivity of aldehydes and ketones 142 8.3.2 Types of nucleophiles 142 8.3.3 Nucleophilic addition of hydride:reduction 143 8.3.4 Nucleophilic addition of carbon nucleophiles formation of C-C honds 146 8.3.5 Nucleophilic addition of oxygen nucleophiles: formation of hydrates and acetals 149 8.3.6 Nucleophilic addition of sulfur nucleophilesa formation of thioacetals 151 8.3.7 Nucleophilic addition of amine nucleophiles: formation of imines and enamines 1526.2.1 Preparation 97 6.2.2 Reactions 98 6.3 Alkynes 110 6.3.1 Preparation 110 6.3.2 Reactions 110 Worked example 113 Problems 114 7 Benzenes 117 7.1 Structure 117 7.2 Reactions 119 7.2.1 Halogenation 119 7.2.2 Nitration 120 7.2.3 Sulfonation 120 7.2.4 Alkylation: The Friedel-Crafts alkylation 121 7.2.5 Acylation: The Friedel-Crafts acylation 122 7.3 Reactivity of substituted benzenes 123 7.3.1 Reactivity of benzene rings: Activating and deactivating substituents 124 7.3.2 Orientation of reactions 125 7.4 Nucleophilic aromatic substitution (the SNAr mechanism) 127 7.5 The formation of benzyne 128 7.6 Transformation of side chains 129 7.7 Reduction of the benzene ring 132 7.8 The synthesis of substituted benzenes 132 7.9 Electrophilic substitution of naphthalene 135 7.10 Electrophilic substitution of pyridine 135 7.11 Electrophilic substitution of pyrrole, furan and thiophene 136 Worked example 136 Problems 137 8 Carbonyl compounds: aldehydes and ketones 139 8.1 Structure 139 8.2 Reactivity 140 8.3 Nucleophilic addition reactions 142 8.3.1 Relative reactivity of aldehydes and ketones 142 8.3.2 Types of nucleophiles 142 8.3.3 Nucleophilic addition of hydride: reduction 143 8.3.4 Nucleophilic addition of carbon nucleophiles: formation of C
C bonds 146 8.3.5 Nucleophilic addition of oxygen nucleophiles: formation of hydrates and acetals 149 8.3.6 Nucleophilic addition of sulfur nucleophiles: formation of thioacetals 151 8.3.7 Nucleophilic addition of amine nucleophiles: formation of imines and enamines 152 Contents vii