Catalytic Hydrogenation over Platinum Metals

Catalytic Hydrogenation over Platinum Metals focuses on catalytic hydrogenation as an effective process in attaining controlled transformations of organic compounds. Composed of contributions of various authors, the book first provides information on catalysts, equipment, and conditions. Catalyst stability and reuse; types of catalyst; platinum metals; and synergism are covered. The text proceeds with discussions on hydrogenation reactors. Topics include atmospheric pressure reactors; low pressure reactors; microreactors; and high pressure reactors. The book also covers hydrogenation of carbon-carbon unsaturation. Catalytic metal; modified catalyst systems; stereochemistry; diacetylenes; and hydrogenolysis are discussed. The text also looks at the hydrogenation of aromatics, nitrogen and carbonyl compounds, and hydrogenolysis. Numerical representations and analysis, diagrams, and reactions of compounds when exposed to different laboratory conditions are considered. The selection is a great source of data for readers interested in studying the process of catalytic hydrogenation.

Preface

Part I Catalysts, Equipment, and Conditions

1 Platinum Metal Catalysts

I. Platinum Metals

II. Types of Catalyst

III. Synergism

IV. Catalyst Stability

V. Safety

VI. Catalyst Reuse

VII. Induction Periods

VIII. Reproducibility of Catalysts

IX. Inhibitors and Poisons

X. Promoters

XI. Preparation of Catalysts

References

2 Hydrogenation Reactors

I. Atmospheric Pressure Reactors

II. Low Pressure Reactors

III. Microreactors

IV. High Pressure Reactors

References

3 Reaction Conditions

I. Temperature

II. Amount of Catalyst

III. Pressure

IV. Agitation

V. Mode of Addition

VI. Solvents

References

Part II Hydrogenation of Carbon-Carbon Unsaturation

4 Acetylenes

I. Catalytic Metal

II. Modified Catalyst Systems

III. Stereochemistry

IV. Diacetylenes

V. Vinylacetylenes

VI. Hydrogenolysis

References

5 Olefins

I. Catalysts

II. Effect of Solvent

III. Effect of Olefin Structure

IV. Double-Bond Migration

V. Stereochemistry

VI. Olefin Saturation in Polyfunctional Molecules

References

Part III Hydrogenation of Nitrogen Compounds

6 Imines

I. Acidic Media

II. Neutral or Basic Media

III. Effect of Structure

References

7 Azines

I. Solvents

II. Preparation of Azo Compounds

References

8 Hydrazones

I. Hydrogenolysis

II. Disproportionation

III. Hydrazines by Reductive Alkylation

References

9 Oximes

I. Catalysts

II. Substrate

III. Solvent

IV. Products of Partial Reduction

V. Oximino Ketones

VI. Products of Interaction with Other Functions

VII. Stereochemistry

References

10 Nitroso Compounds

I. Hydroxylamine

II. N-Nitrosoamines

III. C-Nitroso Compounds

References

11 Nitro Compounds

I. Catalysts

II. Solvents

III. Reduction of the Aromatic Nitro Group to the Amine

IV. Reduction of Aliphatic Nitro Groups to the Amine

V. Difunctional Compounds

VI. Rearrangements

VII. Loss of Nitrogen by Hydrogenolysis

VIII. Products of Partial Reduction

References

12 Nitriles

I. Coupling Reactions: Secondary and Tertiary Amines

II. Products of Reductive Hydrolysis

III. Nitriles with Other Functional Groups

References

Part IV Carbonyl Compounds

13 Hydrogenation of Acids, Esters, and Anhydrides

I. Acids

II. Esters

III. Anhydrides

References

14 Hydrogenation of Aldehydes

I. Saturated Aliphatic Aldehydes

II. Aromatic Aldehydes

III. Unsaturated Aldehydes

References

15 Hydrogenation of Ketones

I. Aliphatic Ketones

II. Aromatic Ketones

III. Stereochemistry

References

16 Reductive Alkylation-Preparation of Amines

I. Substrates

II. Catalysts

III. Stereochemistry

IV. Incipient Amine and Carbonyl Compounds

References

17 Reductive Alkylation-Alkylidene Derivatives

Text

References

Part V Hydrogenation of Aromatics

18 Carbocyclic Aromatics

I. Comparison of Catalysts

II. Partial Reduction of Aromatic Rings

III. Strained Rings

IV. Selective Hydrogenation

V. Reduction of Benzyl Compounds

VI. Fused Rings

VII. Stereochemistry

References

19 Phenols and Phenyl Ethers

I. Platinum Metals

II. Effect of Catalyst and Temperature on Stereochemistry

III. Hydrogenolysis without Ring Reduction

IV. Partial Ring Reduction

V. Ring Saturation without Hydrogenolysis

VI. Ring Reduction with Hydrogenolysis

References

20 Anilines

I. Reduction to the Saturated Amine

II. Secondary Amines

III. Hydrogenolysis

IV. Hydrolysis

References

21 Furans

I. Hydrogenation of the Furan Nucleus

II. Hydrogenolysis of Furans

References

22 Nitrogen Heterocyclic Compounds

I. Pyrroles

II. Indoles

III. Pyridines

IV. Quinolines and Isoquinolines

V. Imidazoles

VI. Pyridazines

VII. Pyrazines

VIII. Pyrimidines

References

Part VI Hydrogenolysis

23 Hydrogenation of Acid Chlorides—Rosenmund Reduction

I. Catalyst Regulators

II. Side-Reactions

III. Procedure

IV. Selective Hydrogenation

References

24 Catalytic Dehalogenation

I. Catalysts

II. Dehalogenation in Basic Media

III. Choice of Base

IV. Halogen Compounds with Other Functions

V. Selective Hydrogenation of Polyhalo Compounds

VI. Rearrangements

VII. Coupling Reactions

VIII. Dehalogenation with Hydrazine

References

25 Miscellaneous Hydrogenolyses

I. Allylic Oxygen

II. Allylic Nitrogen

III. Vinyl Functions

IV. Debenzylation

V. Hydrogenolysis of the Carbon-Carbon Bond

VI. Hydrogenolysis of the Carbon-Oxygen Bond

VII. Hydrogenolysis of the Carbon-Nitrogen Bond

VIII. Hydrogenolysis of the Nitrogen-Oxygen Bond

IX. Hydrogenolysis of the Oxygen-Oxygen Bond

X. Hydrogenolysis of the Nitrogen-Nitrogen Bond

References

Author Index

Subject Index