viii
CONTENTS
7.5
Hydride as a nucleophile: reduction of aldehydes and ketones,
lithium aluminium hydride and sodium borohydride
235
7.6
Carbon as a nucleophile
238
7.6.1
Cyanide: cyanohydrins
238
7.6.2
Organometallics: Grignard reagents and acetylides
240
7.7
Nitrogen as a nucleophile: imines and enamines
242
7.7.1
Imines
242
7.7.2
Enamines
247
7.8
Nucleophilic substitution on carbonyl groups: carboxylic acid derivatives
248
7.9
Oxygen and sulfur as nucleophiles: esters and carboxylic acids
252
7.9.1
Alcohols: ester formation
252
7.9.2
Water: hydrolysis of carboxylic acid derivatives
256
7.9.3
Thiols: thioacids and thioesters
261
7.10 Nitrogen as a nucleophile: amides
262
7.11 Hydride as a nucleophile: reduction of carboxylic acid derivatives
267
7.12 Carbon as a nucleophile: Grignard reagents
271
7.13 Nucleophilic substitution on derivatives of sulfuric and phosphoric acids
272
7.13.1
Sulfuric acid derivatives
272
7.13.2
Phosphoric acid derivatives
275
8
Electrophilic reactions
283
8.1
Electrophilic addition to unsaturated carbon
283
8.1.1
Addition of hydrogen halides to alkenes
284
8.1.2
Addition of halogens to alkenes
286
8.1.3
Electrophilic additions to alkynes
292
8.1.4
Carbocation rearrangements
296
8.2
Electrophilic addition to conjugated systems
296
8.3
Carbocations as electrophiles
299
8.4
Electrophilic aromatic substitution
304
8.4.1
Electrophilic alkylations: Friedel–Crafts reactions
306
8.4.2
Electrophilic acylations: Friedel–Crafts reactions
308
8.4.3
Effect of substituents on electrophilic aromatic substitution
309
8.4.4
Electrophilic substitution on polycyclic aromatic compounds
315
9
Radical reactions
319
9.1
Formation of radicals
319
9.2
Structure and stability of radicals
321
9.3
Radical substitution reactions: halogenation
322
9.3.1
Stereochemistry of radical reactions
325
9.3.2
Allylic and benzylic substitution: halogenation reactions
325
9.4
Radical addition reactions: addition of HBr to alkenes
328
9.4.1
Radical addition of HBr to conjugated dienes
330
9.4.2
Radical polymerization of alkenes
331
9.4.3
Addition of hydrogen to alkenes and alkynes: catalytic
hydrogenation
332
9.5
Radical addition of oxygen: autoxidation reactions
333
9.6
Phenolic oxidative coupling
340
CONTENTS
7.5
Hydride as a nucleophile: reduction of aldehydes and ketones,
lithium aluminium hydride and sodium borohydride
235
7.6
Carbon as a nucleophile
238
7.6.1
Cyanide: cyanohydrins
238
7.6.2
Organometallics: Grignard reagents and acetylides
240
7.7
Nitrogen as a nucleophile: imines and enamines
242
7.7.1
Imines
242
7.7.2
Enamines
247
7.8
Nucleophilic substitution on carbonyl groups: carboxylic acid derivatives
248
7.9
Oxygen and sulfur as nucleophiles: esters and carboxylic acids
252
7.9.1
Alcohols: ester formation
252
7.9.2
Water: hydrolysis of carboxylic acid derivatives
256
7.9.3
Thiols: thioacids and thioesters
261
7.10 Nitrogen as a nucleophile: amides
262
7.11 Hydride as a nucleophile: reduction of carboxylic acid derivatives
267
7.12 Carbon as a nucleophile: Grignard reagents
271
7.13 Nucleophilic substitution on derivatives of sulfuric and phosphoric acids
272
7.13.1
Sulfuric acid derivatives
272
7.13.2
Phosphoric acid derivatives
275
8
Electrophilic reactions
283
8.1
Electrophilic addition to unsaturated carbon
283
8.1.1
Addition of hydrogen halides to alkenes
284
8.1.2
Addition of halogens to alkenes
286
8.1.3
Electrophilic additions to alkynes
292
8.1.4
Carbocation rearrangements
296
8.2
Electrophilic addition to conjugated systems
296
8.3
Carbocations as electrophiles
299
8.4
Electrophilic aromatic substitution
304
8.4.1
Electrophilic alkylations: Friedel–Crafts reactions
306
8.4.2
Electrophilic acylations: Friedel–Crafts reactions
308
8.4.3
Effect of substituents on electrophilic aromatic substitution
309
8.4.4
Electrophilic substitution on polycyclic aromatic compounds
315
9
Radical reactions
319
9.1
Formation of radicals
319
9.2
Structure and stability of radicals
321
9.3
Radical substitution reactions: halogenation
322
9.3.1
Stereochemistry of radical reactions
325
9.3.2
Allylic and benzylic substitution: halogenation reactions
325
9.4
Radical addition reactions: addition of HBr to alkenes
328
9.4.1
Radical addition of HBr to conjugated dienes
330
9.4.2
Radical polymerization of alkenes
331
9.4.3
Addition of hydrogen to alkenes and alkynes: catalytic
hydrogenation
332
9.5
Radical addition of oxygen: autoxidation reactions
333
9.6
Phenolic oxidative coupling
340