A
Guide to Organic Chemistry Mechanisms
Table of Contents
Acknowledgements - iii
To the Instructor - iv
To the Student - iv
Table of Contents - v
Index - vii
Preface
About the Book - xiii
The Curved Arrow - xiv
Rules for Pushing Electrons - xiv
1 - Getting Ready for Reactions
About the Atom - 1
Guide to Drawing Resonance Structures - 2
Resonance Structures of Anions - 2
Resonance Structures of Cations - 3
Resonance Structures of Neutral Compounds with
Non-Bonded Electrons - 4
Resonance Structures of Neutral Compounds without
Non-Bonded Electrons - 5
Resonance Structures of Radicals - 6
2 - Acid-Base Chemistry
Bronsted-Lowrey Acids and Bases - 7
Lewis Acids and Bases - 11
3 - Substitution Reactions
SN2
Substitution Reactions - 12
SN1
Substitution Reactions - 16
4 - Elimination Reactions
Alkene Formation - 18
Acetylene Formation - 23
5 - Electrophilic Addition to Alkenes and
Alkynes
Carbon-Carbon Double Bond Reactions
Addition of HX and H2O to Alkenes - 24
Bromination - 27
Oxymercuration - 28
Hydroboration-Oxidation of Alkene - 29
Carbon-Carbon Triple Bond Reactions
Addition to an Internal Acetylene - 31
Addition to a Terminal Acetylene - 32
Disiamylborane Hydroboration-Oxidation of an Acetylene
- 33
6 - Rearrangement Reactions
Baeyer-Villiger Oxidation - 34
Pinacol Rearrangement - 36
Benzilic Acid Rearrangement - 36
Dakin Reaction - 37
Acetone from Cumene - 37
7 - Electrocyclic Reactions
Diels Alder Reactions - 38
Other Electrocyclic Reactions - 41
8 - Carbonyl Addition and
Addition-Elimination Reactions
Grignard Addition to a Carbonyl Group - 42
Alkyllithium Addition to a Carbonyl Group -
42
Wittig Reaction - 43
Addition-Elimination Reactions (Reversible Additions)
- 44
Ketal Formation and Hydrolysis - 44
Oxime Formation - 45
Other Additions to a Carbonyl Group - 45
Reactions of Acyl Chlorides, Anhydrides, Esters, and
Amides - 46
Esters from Acid Chlorides or Anhydrides -
46
Amides from Acid Chlorides or Anhydrides -
47
Ester from Acid with Mineral Acid Catalysis
(Fischer Esterification) - 48
Acid Catalyzed Hydrolysis of an Ester - 48
Base Hydrolysis of an Ester (Saponification) - 49
Hydrolysis of an Amide - 49
Reactions of Esters - 50
Reactions of Nitriles - 51
Miscellaneous, Ester with Diazomethane - 52
9 - Reactions of Enols and Enolates
Aldol Reaction - 53
Claisen Condensation - 55
Acetoacetate Synthesis - 56
Enolate Alkylation Reactions - 57
Halogenation of Carbonyl Compounds - 58
Michael or 1,4-Conjugate Addition Reaction-59
Enamine Alkylation - 60
10 - Dehydration/Halogenation Agents
Carboxylic Acid with Thionyl Chloride - 62
Alcohol with a Phosphorus Reagent - 63
11 - Reduction Reactions
Sodium Borohydride Reductions - 64
Lithium Aluminum Hydride Reductions - 65
Reductive Amination - 67
Diisobutylaluminum Hydride Reduction - 68
Reduction of Alkyne with Sodium/NH3
- 68
Wolff Kischner Reduction - 69
Catalytic Reduction of Nitrobenzene - 69
12 - Oxidation-Reactions
General Form For Oxidations - 70
Chromic Acid Oxidation - 70
PCC, Tollens, Hypochlorite, and Sulfonium Based
Oxidations - 71
Peracid Epoxidation, MCPBA - 71
Ozone Oxidation - 73
Osmium Tetroxide, Permanganate, and Periodate
Oxidations - 74
13 - Organometallic Reactions
Acyclic Heck Reaction - 75
Cyclic Heck Reaction - 76
Catalytic Reduction of an Alkene - 77
Gilman Reagent - 77
14 - Aromatic Substitution Reactions
Electrophilic Aromatic Substitution, of Benzene -
78
Electrophilic Aromatic Substitution of Substituted
Aromatic Compounds - 79
Nucleophilic Aromatic Substitution - 81
Benzyne Reaction - 81
Diazonium Chemistry - 82
15 - Carbene and Nitrene Reactions
Carbene Reactions - 83
Curtius Rearrangement - 84
Hoffmann Rearrangement - 85
16 - Radical Reactions
Free Radical Bromination Reaction - 86
Allylic Bromination with NBS - 87
Radical Addition of Hydrogen Bromide - 88
Benzylic Bromination with NBS - 89
Notes
Notes to Specific Reactions - Notes 1-26