Page 20 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

xx 10.6.3. Overview of [3,3]-Sigmatropic Rearrangements ................. 919
10.6.4. [2,3]-Sigmatropic Rearrangements....................................... 939
Contents
Topic 10.1. Application of DFT Concepts to Reactivity and Regiochemistry
of Cycloaddition Reactions............................................................... 945
Problems ................................................................................................................. 951

Chapter 11. Free Radical Reactions ..................................... 965

Introduction ............................................................................................................ 965
11.1. Generation and Characterization of Free Radicals...................................... 967
11.1.1. Background ..................................................................................... 967
11.1.2. Long-Lived Free Radicals .............................................................. 968
11.1.3. Direct Detection of Radical Intermediates..................................... 970
11.1.4. Generation of Free Radicals ........................................................... 976
11.1.5. Structural and Stereochemical Properties of Free Radicals........... 980
11.1.6. Substituent Effects on Radical Stability......................................... 986
11.1.7. Charged Radicals ............................................................................ 988
11.2. Characteristics of Reactions Involving Radical Intermediates ................... 992
11.2.1. Kinetic Characteristics of Chain Reactions.................................... 992
11.2.2. Determination of Reaction Rates.................................................... 995
11.2.3. Structure-Reactivity Relationships ................................................. 1000
11.3. Free Radical Substitution Reactions............................................................ 1018
11.3.1. Halogenation ................................................................................... 1018
11.3.2. Oxygenation .................................................................................... 1024
11.4. Free Radical Addition Reactions................................................................. 1026
11.4.1. Addition of Hydrogen Halides ....................................................... 1026
11.4.2. Addition of Halomethanes.............................................................. 1029
11.4.3. Addition of Other Carbon Radicals................................................ 1031
11.4.4. Addition of Thiols and Thiocarboxylic Acids ............................... 1033
11.4.5. Examples of Radical Addition Reactions....................................... 1033
11.5. Other Types of Free Radical Reactions....................................................... 1037
11.5.1. Halogen, Sulfur, and Selenium Group Transfer Reactions ........... 1037
11.5.2. Intramolecular Hydrogen Atom Transfer Reactions...................... 1040
11.5.3. Rearrangement Reactions of Free Radicals.................................... 1041
11.6. S 1 Substitution Processes......................................................................... 1044
RN
11.6.1. S 1 Substitution Reactions of Alkyl Nitro Compounds.............. 1045
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11.6.2. S 1 Substitution Reactions of Aryl and Alkyl Halides............... 1048
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Topic 11.1. Relationships between Bond and Radical
Stabilization Energies........................................................................ 1052
Topic 11.2. Structure-Reactivity Relationships in Hydrogen Abstraction
Reactions............................................................................................ 1056
General References................................................................................................. 1062
Problems ................................................................................................................. 1063

Chapter 12. Photochemistry ............................................. 1073

Introduction............................................................................................................. 1073
12.1. General Principles ........................................................................................ 1073