Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis

by
Edition: 1st
Format: Hardcover
Pub. Date: 2001-04-17
Publisher(s): Wiley-Interscience
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Summary

The most comprehensive reference in the field, Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis provides synthetic chemists and chemical engineers in fine chemicals and pharmaceuticals with detailed experimental guidelines for heterogeneous catalytic hydrogenation. Organized by functional groups for ready reference and featuring detailed examples of hundreds of reactions, this handbook covers hydrogenations of alkenes, alkynes, aldehydes and ketones, nitriles, imines, nitro and nitroso compounds, carboxylic acids and esters, and aromatic and heterocyclic compounds. In addition, coverage includes the preparation of amines by reductive alkylation and the hydrogenolysis of a variety of compounds. Examples of hydrogenation of functional groups and reaction pathways are illustrated with numerous equations and schemes.Practitioners will appreciate the plenitude of experimental details given for most of the reactions selected, including amounts of reagents and catalysts, reaction temperatures, hydrogen pressures, and reaction times. They will also find helpful the more than one hundred tables included throughout the book detailing the effects of key factors governing rate and selectivity, such as compound structure, the nature of catalysts and supports, and the nature of solvents. Researchers will benefit from the introductory chapters covering an array of hydrogenation catalysts, including nickel, cobalt, copper, iron, platinum group metals, rhenium, and other oxide and sulfide catalysts, as well as reactors and reaction conditions.

Author Biography

SHIGEO NISHIMURA, DSc, is Professor Emeritus at the Tokyo University of Agriculture and Technology. He is a member of the Chemical Society of Japan and the Catalysis Society of Japan.

Table of Contents

Preface xi
Hydrogenation Catalysts
1(51)
Nickel Catalysts
2(21)
Reduced Nickel
3(2)
Nickel from Nickel Formate
5(2)
Raney Nickel
7(12)
Urushibara Nickel
19(1)
Nickel Boride
20(3)
Cobalt Catalysts
23(3)
Reduced Cobalt
23(1)
Raney Cobalt
24(1)
Cobalt Boride
25(1)
Urushibara Cobalt
26(1)
Copper Catalysts
26(2)
Iron Catalysts
28(1)
Platinum Group Metal Catalysts
29(13)
Platinum
30(4)
Palladium
34(4)
Ruthenium
38(2)
Rhodium
40(1)
Osmium
41(1)
Iridium
42(1)
Rhenium Catalysts
42(1)
The Oxide and Sulfide Catalysts of Transition Metals Other than Rhenium
43(9)
Reactors and Reaction Conditions
52(12)
Reactors
52(1)
Reaction Conditions
53(11)
Inhibitors and Poisons
53(6)
Temperature and Hydrogen Pressure
59(5)
Hydrogenation of Alkenes
64(84)
Isolated Double Bonds: General Aspects
65(3)
Hydrogenation and Isomerization
68(4)
Alkyl-Substituted Ethylenes
72(5)
Selective Hydrogenation of Isolated Double Bonds
77(7)
Fatty Acid Esters and Glyceride Oils
84(8)
Conjugated Double Bonds
92(8)
Aryl-Substituted Ethylenes
92(1)
α,β-Unsaturated Acids and Esters
93(1)
Conjugated Dienes
94(6)
Stereochemistry of the Hydrogenation of Carbon--Carbon Double Bonds
100(19)
Syn and Apparent Anti Addition of Hydrogen
100(5)
Catalyst Hindrance
105(6)
Effects of Polar Groups
111(8)
Selective Hydrogenations in the Presence of Other Functional Groups
119(29)
Isolated Double Bonds in the Presence of a Carbonyl Group
119(3)
Double Bonds Conjugated with a Carbonyl Group
122(7)
Stereochemistry of the Hydrogenation of Δ1,9-2-Octalone and Related Systems
129(7)
An Olefin Moiety in the Presence of Terminal Alkyne Function
136(1)
β-Alkoxy-α,β-Unsaturated Ketones (Vinylogous Esters)
137(11)
Hydrogenation of Alkynes
148(22)
Hydrogenation over Palladium Catalysts
149(11)
Hydrogenation over Nickel Catalysts
160(5)
Hydrogenation over Iron Catalysts
165(5)
Hydrogenation of Aldehydes and Ketones
170(56)
Aldehydes
170(8)
Hydrogenation of Unsaturated Aldehydes to Unsaturated Alcohols
178(7)
Ketones
185(15)
Aliphatic and Alicyclic Ketones
186(4)
Aromatic Ketones
190(3)
Hydrogenation Accompanied by Hydrogenolysis and Cyclization
193(4)
Amino Ketones
197(1)
Unsaturated Ketones
198(2)
Stereochemistry of the Hydrogenation of Ketones
200(18)
Hydrogenation of Cyclohexanones to Axial Alcohols
200(5)
Hydrogenation of Cyclohexanones to Equatorial Alcohols
205(2)
Effects of a Polar Substituent and Heteroatoms in the Ring
207(1)
Alkylcyclopentanones
208(1)
Hindered Ketones
209(3)
Hydrogenation of Fructose
212(1)
Enantioselective Hydrogenations
212(6)
Mechanistic Aspects of the Hydrogenation of Ketones
218(8)
Preparation of Amines by Reductive Alkylation
226(28)
Reductive Alkylation of Ammonia with Carbonyl Compounds
226(10)
Reductive Alkylation of Primary Amines with Carbonyl Compounds
236(5)
Preparation of Tertiary Amines
241(5)
Reductive Alkylation of Amine Precursors
246(1)
Alkylation of Amines with Alcohols
247(1)
Synthesis of Optically Active α-Amino Acids from α-Oxo Acids by Asymmetric Transamination
248(2)
Asymmetric Synthesis of 2-Substituted Cyclohexylamines
250(4)
Hydrogenation of Nitriles
254(32)
General Aspects
254(5)
Hydrogenation to Primary Amines
259(6)
Hydrogenation of Dinitriles to Aminonitriles
265(2)
Hydrogenation to Aldimines or Aldehydes
267(3)
Hydrogenation to Secondary and Tertiary Amines
270(3)
Hydrogenation Accompanied by Side Reactions
273(13)
Aminonitriles
273(2)
Hydroxy- and Alkoxynitriles
275(2)
Hydrogenation Accompanied by Cyclization
277(9)
Hydrogenation of Imines, Oximes, and Related Compounds
286(29)
Imines
286(4)
N-Unsubstituted Imines
286(1)
Aliphatic N-Substituted Imines
287(1)
Aromatic N-Substituted Imines
288(2)
Oximes
290(15)
Hydrogenation to Amines
291(10)
Hydrogenation to Hydroxylamines
301(1)
Hydrogenation Accompanied by Cyclization
302(3)
Hydrazones and Azines
305(10)
Hydrazones
305(5)
Azines
310(5)
Hydrogenation of Nitro, Nitroso, and Related Compounds
315(72)
Hydrogenation of Nitro Compounds: General Aspects
315(1)
Aliphatic Nitro Compounds
315(17)
Hydrogenation Kinetics
315(1)
Hydrogenation to Amines
316(6)
Hydrogenation to Nitroso or Hydroxyimino and Hydroxyamino Compounds
322(5)
Conjugated Nitroalkenes
327(3)
Hydrogenation Accompanied by Cyclization
330(2)
Aromatic Nitro Compounds
332(31)
Hydrogenation to Amines
332(10)
Halonitrobenzenes
342(5)
Hydrogenation of Dinitrobenzenes to Aminonitrobenzenes
347(3)
Selective Hydrogenations in the Presence of Other Unsaturated Functions
350(3)
Hydrogenation Accompanied by Condensation or Cyclization
353(6)
Hydrogenation to Hydroxylamines
359(3)
Hydrogenation to Hydrazobenzenes
362(1)
Nitroso Compounds
363(6)
N-Oxides
369(2)
Other Nitrogen Functions Leading to the Formation of Amino Groups
371(16)
Azo Compounds
371(4)
Diazo Compounds
375(2)
Azides
377(10)
Hydrogenation of Carboxylic Acids, Esters, and Related Compounds
387(27)
Carboxylic Acids
387(5)
Hydrogenation to Alcohols
387(4)
Hydrogenation to Aldehydes
391(1)
Esters, Lactones, and Acid Anhydrides
392(14)
Esters
392(6)
Hydrogenation of Unsaturated Esters to Unsaturated Alcohols
398(1)
Hydrogenation of Esters to Ethers
399(1)
Lactones
399(3)
Acid Anhydrides
402(4)
Acid Amides, Lactams, and Imides
406(8)
Hydrogenation of Aromatic Compounds
414(83)
Aromatic Hydrocarbons
414(13)
Hydrogenation of Benzene to Cyclohexene
419(2)
Hydrogenation of Polyphenyl Compounds to Cyclohexylphenyl Derivatives
421(2)
Stereochemistry of Hydrogenation
423(4)
Phenols and Phenyl Ethers
427(20)
Phenols
427(9)
Hydrogenation to Cyclohexanones
436(5)
Phenyl Ethers
441(6)
Aromatic Compounds Containing Benzyl--Oxygen Linkages
447(7)
Carboxylic Acids and Esters
454(5)
Arylamines
459(10)
Naphthalene and Its Derivatives
469(8)
Anthracene, Phenathrene, and Related Compounds
477(5)
Other Polynuclear Compounds
482(15)
Hydrogenation of Heterocyclic Aromatic Compounds
497(75)
N-Heterocycles
497(50)
Pyrroles
497(3)
Indoles and Related Compounds
500(4)
Pyridines
504(14)
Quinolines, Isoquinolines, and Related Compounds
518(14)
Polynuclear Compounds Containing a Bridgehead Nitrogen
532(2)
Polynuclear Compounds with More than One Nitrogen Ring
534(2)
Compounds with More than One Nitrogen Atom in the Same Ring
536(11)
O-Heterocycles
547(15)
Furans and Related Compounds
547(7)
Pyrans, Pyrones, and Related Compounds
554(8)
S-Heterocycles
562(10)
Hydrogenolysis
572(92)
Hydrogenolysis of Carbon--Oxygen Bonds
572(29)
Alcohols and Ethers
572(3)
Epoxy Compounds
575(8)
Benzyl-Oxygen Functions
583(11)
Stereochemistry of the Hydrogenolysis of Benzyl--Oxygen Compounds
594(4)
Vinyl--Oxygen Compounds
598(3)
Hydrogenolysis of Carbon--Nitrogen Bonds
601(6)
Hydrogenolysis of Organic Sulfur Compounds
607(16)
Thiols
610(3)
Thioethers
613(1)
Hemithioacetals
614(2)
Dithioacetals
616(1)
Thiophenes
617(1)
Thiol Esters and Thioamides
618(1)
Disulfides
618(1)
Hydrogenolysis over Metal Sulfide Catalysts
619(1)
Sulfones, Sulfonic Acids, and Their Derivatives
620(2)
Stereochemistry of the Desulfurization with Raney Nickel
622(1)
Hydrogenolysis of Carbon--Halogen Bonds
623(17)
R--X Bonds at Saturated Carbons
623(6)
Activated Alkyl and Cycloalkyl Halides
629(2)
Allyl and Vinyl Halides
631(2)
Benzyl and Aryl Halides
633(4)
Halothiazoles
637(1)
Hydrogenolysis of Acid Chlorides to Aldehydes (the Rosenmund Reduction)
638(2)
Hydrogenolysis of Carbon--Carbon Bonds
640(11)
Cyclopropanes
640(7)
Cyclobutanes
647(1)
Open-Chain Carbon--Carbon Bonds
647(4)
Miscellaneous Hydrogenolyses
651(13)
Nitrogen--Oxygen and Nitrogen--Nitrogen Bonds
651(2)
Oxygen--Oxygen Bonds
653(11)
General Bibliography 664(1)
Author Index 665(14)
Subject Index 679

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