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
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