Page 16 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

xvi 3.8. Solvent Effects ............................................................................................... 359
3.8.1. Bulk Solvent Effects........................................................................... 359
Contents
3.8.2. Examples of Specific Solvent Effects................................................ 362
Topic 3.1. Acidity of Hydrocarbons..................................................................... 368
General References................................................................................................. 376
Problems ................................................................................................................. 376

Chapter 4. Nucleophilic Substitution ................................... 389

Introduction ............................................................................................................ 389
4.1. Mechanisms for Nucleophilic Substitution ................................................... 389
4.1.1. Substitution by the Ionization S 1 Mechanism.............................. 391
N
4.1.2. Substitution by the Direct Displacement
S 2 Mechanism............................................................................... 393
N
4.1.3. Detailed Mechanistic Description
and Borderline Mechanisms............................................................... 395
4.1.4. Relationship between Stereochemistry and Mechanism
of Substitution..................................................................................... 402
4.1.5. Substitution Reactions of Alkyldiazonium Ions ................................ 405
4.2. Structural and Solvation Effects on Reactivity............................................. 407
4.2.1. Characteristics of Nucleophilicity...................................................... 407
4.2.2. Effect of Solvation on Nucleophilicity .............................................. 411
4.2.3. Leaving-Group Effects ....................................................................... 413
4.2.4. Steric and Strain Effects on Substitution
and Ionization Rates ........................................................................... 415
4.2.5. Effects of Conjugation on Reactivity................................................. 417
4.3. Neighboring-Group Participation .................................................................. 419
4.4. Structure and Reactions of Carbocation Intermediates................................. 425
4.4.1. Structure and Stability of Carbocations ............................................. 425
4.4.2. Direct Observation of Carbocations................................................... 436
4.4.3. Competing Reactions of Carbocations............................................... 438
4.4.4. Mechanisms of Rearrangement of Carbocations ............................... 440
4.4.5. Bridged (Nonclassical) Carbocations................................................. 447
Topic 4.1. The Role Carbocations and Carbonium Ions in Petroleum
Processing ............................................................................................ 454
General References................................................................................................. 459
Problems ................................................................................................................. 459

Chapter 5. Polar Addition and Elimination Reactions ................... 473

Introduction............................................................................................................. 475
5.1. Addition of Hydrogen Halides to Alkenes.................................................. 476
5.2. Acid-Catalyzed Hydration and Related Addition Reactions ...................... 482
5.3. Addition of Halogens................................................................................... 485
5.4. Sulfenylation and Selenenylation ................................................................ 497
5.4.1. Sulfenylation..................................................................................... 498
5.4.2. Selenenylation................................................................................... 500
5.5. Addition Reactions Involving Epoxides...................................................... 503
5.5.1. Epoxides from Alkenes and Peroxidic Reagents............................. 503
5.5.2. Subsequent Transformations of Epoxides........................................ 511