Catalytic Hydrogenation in Organic Syntheses

Catalytic Hydrogenation in Organic Syntheses focuses on the process of catalytic hydrogenation in organic synthesis. This book gives the reader easy access to catalytic history, to show what can be done and how to do it. A variety of working generalities and common sense guides are given as aids in selecting catalytic metal, catalyst support, concentration of metal and catalyst, solvent, and reaction conditions. All manner of hydrogenation catalysts are considered and mechanisms of hydrogenation are presented at a level that is useful to the synthetic organic chemist. This volume is comprised of 15 chapters and begins with an overview of catalytic hydrogenation and heterogeneous hydrogenation catalysts, along with hydrogenation reactors and reaction conditions. The discussion then shifts to the hydrogenation of compounds such as acetylenes, olefins, aldehydes, ketones, nitriles, oximes, acids, esters, lactones, anhydrides, and nitro compounds as well as carbocyclic aromatics and heterocyclic compounds. The reader is also introduced to reductive alkylation, catalytic dehydrohalogenation, and hydrogenolysis of small rings. A chapter on miscellaneous hydrogenolyses concludes the book. This book will be of interest to organic chemists working in the field of catalytic hydrogenation.

Preface

Chapter 1 Hydrogenation Catalysts, Reactors, and Reaction Conditions

I. General Considerations

II. Reaction Conditions and Catalyst Variables

III. Hydrogenation Reactors

IV. Preparation of Catalysts

References

Chapter 2 Hydrogenation of Acetylenes

I. General Considerations

II. Catalysts

III. Acetylenic Carbinols and Glycols

IV. Hydrogenolysis

V. Acetylenic Aldehydes and Ketones

VI. Polyacetylenes

References

Chapter 3 Hydrogenation of Olefins

I. Mechanism of Hydrogenation

II. Catalysts

III. Effect of Olefin Structure

IV. Double-Bond Migration

V. Effects of Double-Bond Migration

VI. Cis-Trans Isomerization

VII. Stereochemistry

VIII. Vinyl Functions

IX. Unsaturated Carbonyl Compounds

References

Chapter 4 Hydrogenation of Acids, Esters, Lactones, and Anhydrides

I. Hydrogenation of Acids

II. Hydrogenolysis of Esters

III. Hydrogenation of Lactones

IV. Hydrogenation of Anhydrides

References

Chapter 5 Hydrogenation of Aldehydes

I. Saturated Aliphatic Aldehydes

II. Unsaturated Aliphatic Aldehydes

III. Aromatic Aldehydes

IV. Aromatic Unsaturated Aldehydes

References

Chapter 6 Hydrogenation of Ketones

I. Aliphatic Ketones

II. Aromatic Ketones

References

Chapter 7 Hydrogenation of Nitro Compounds

I. Catalysts

II. Solvents

III. Partial Reduction of Nitro Compounds

IV. Reduction of Aliphatic Nitro Compounds

V. Unsaturated Nitro Compounds

VI. Halonitro Aromatics

VII. Dinitro Compounds

VIII. Cyclizations

References

Chapter 8 Hydrogenation of Nitriles

I. Mechanism

II. Catalysts

III. Unsymmetrical Amines

IV. Cyclizations

V. Reductive Hydrolysis

VI. Methylation

References

Chapter 9 Hydrogenation of Oximes

I. Catalysts

II. Substrates

III. Solvent

IV. Products of Partial Reduction

V. Products of Hydrolysis

VI. Bifunctional Molecules

VII. Stereochemistry

References

Chapter 10 Reductive Alkylation

I. Substrates

II. Catalysts

III. Stereochemistry

References

Chapter 11 Hydrogenation of Carbocyclic Aromatics

I. Carbocyclic Aromatics

II. Anilines

III. Phenols and Phenyl Ethers

References

Chapter 12 Hydrogenation of Heterocyclic Compounds

I. Pyridines

II. Pyrroles

III. Indoles

IV. Quinolines and Isoquinolines

V. Imidazoles and Imidazolones

VI. Pyrazines

VII. Pyrimidines

VIII. Furans

References

Chapter 13 Catalytic Dehydrohalogenation

I. Catalysts

II. Basic Media

III. Effect of Structure

IV. Elimination Reactions

V. Halohydrins

VI. Haloolefins

VII. Halonitro Compounds

VIII. Polyhalo Compounds

IX. Halogen as Blocking Group

X. Trapping Reactions

References

Chapter 14 Hydrogenolysis of Small Rings

I. Cyclopropanes

II. Oxiranes

III. Aziridines

References

Chapter 15 Miscellaneous Hydrogenolyses

I. Benzyl Groups Attached to Oxygen

II. Benzyl Groups Attached to Nitrogen

III. Allylic Oxygen Compounds

IV. Hydrogenolysis of the Carbon-Carbon Bond

V. Hydrogenolysis of the Oxygen-Oxygen Bond

VI. Hydrogenolysis of the Nitrogen-Oxygen Bond

VII. Hydrogenolysis of the Nitrogen-Nitrogen Bond

References

Index