Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis

Shigeo Nishimura0-471-39698-2, 9780471396987

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.

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Table of contents :
000 – 1157_fm.pdf……Page 1
Author Index……Page 0
Preface……Page 3
Table of Contents……Page 5
1. Hydrogenation Catalysts……Page 11
1.1 Nickel Catalysts……Page 12
1.1.1 Reduced Nickel……Page 13
1.1.2 Nickel from Nickel Formate……Page 15
1.1.3 Raney Nickel……Page 17
1.1.4 Urushibara Nickel……Page 29
1.1.5 Nickel Boride……Page 30
1.2.1 Reduced Cobalt……Page 33
1.2.2 Raney Cobalt……Page 34
1.2.3 Cobalt Boride……Page 35
1.3 Copper Catalysts……Page 36
1.4 Iron Catalysts……Page 38
1.5 Platinum Group Metal Catalysts……Page 39
1.5.1 Platinum……Page 40
1.5.2 Palladium……Page 44
1.5.3 Ruthenium……Page 48
1.5.4 Rhodium……Page 50
1.5.5 Osmium……Page 51
1.6 Rhenium Catalysts……Page 52
1.7 The Oxide and Sulfide Catalysts of Transition Metals Other than Rhenium……Page 53
2.1 Reactors……Page 62
2.2.1 Inhibitors and Poisons……Page 63
2.2.2 Temperature and Hydrogen Pressure……Page 69
3. Hydrogenation of Alkenes……Page 74
3.1 Isolated Double Bonds: General Aspects……Page 75
3.2 Hydrogenation and Isomerization……Page 78
3.3 Alkyl-Substituted Ethylenes……Page 82
3.4 Selective Hydrogenation of Isolated Double Bonds……Page 87
3.5 Fatty Acid Esters and Glyceride Oils……Page 94
3.6.1 Aryl-Substituted Ethylenes……Page 102
3.6.2 alpha,beta-Unsaturated Acids and Esters……Page 103
3.6.3 Conjugated Dienes……Page 104
3.7.1 Syn and Apparent Anti Addition of Hydrogen……Page 110
3.7.2 Catalyst Hindrance……Page 115
3.7.3 Effects of Polar Groups……Page 121
3.8.1 Isolated Double Bonds in the Presence of a Carbonyl Group……Page 129
3.8.2 Double Bonds Conjugated with a Carbonyl Group……Page 132
3.8.3 Stereochemistry of the Hydrogenation of Delta 1,9-2-Octalone and Related Systems……Page 139
3.8.4 An Olefin Moiety in the Presence of Terminal Alkyne Function……Page 146
3.8.5 beta-Alkoxy-alpha,beta-Unsaturated Ketones (Vinylogous Esters)……Page 147
4. Hydrogenation of Alkynes……Page 158
4.1 Hydrogenation over Palladium Catalysts……Page 159
4.2 Hydrogenation over Nickel Catalysts……Page 170
4.3 Hydrogenation over Iron Catalysts……Page 175
5.1 Aldehydes……Page 180
5.2 Hydrogenation of Unsaturated Aldehydes to Unsaturated Alcohols……Page 188
5.3 Ketones……Page 195
5.3.1 Aliphatic and Alicyclic Ketones……Page 196
5.3.2 Aromatic Ketones……Page 200
5.3.3 Hydrogenation Accompanied by Hydrogenolysis and Cyclization……Page 203
5.3.4 Amino Ketones……Page 207
5.3.5 Unsaturated Ketones……Page 208
5.4.1 Hydrogenation of Cyclohexanones to Axial Alcohols……Page 210
5.4.2 Hydrogenation of Cyclohexanones to Equatorial Alcohols……Page 215
5.4.3 Effects of a Polar Substituent and Heteroatoms in the Ring……Page 217
5.4.4 Alkylcyclopentanones……Page 218
5.4.5 Hindered Ketones……Page 219
5.4.7 Enantioselective Hydrogenations……Page 222
5.5 Mechanistic Aspects of the Hydrogenation of Ketones……Page 228
6.1 Reductive Alkylation of Ammonia with Carbonyl Compounds……Page 236
6.2 Reductive Alkylation of Primary Amines with Carbonyl Compounds……Page 246
6.3 Preparation of Tertiary Amines……Page 251
6.4 Reductive Alkylation of Amine Precursors……Page 256
6.5 Alkylation of Amines with Alcohols……Page 257
6.6 Synthesis of Optically Active alpha-Amino Acids from alpha-Oxo Acids by Asymmetric Transamination……Page 258
6.7 Asymmetric Synthesis of 2-Substituted Cyclohexylamines……Page 260
7.1 General Aspects……Page 264
7.2 Hydrogenation to Primary Amines……Page 269
7.3 Hydrogenation of Dinitriles to Aminonitriles……Page 275
7.4 Hydrogenation to Aldimines or Aldehydes……Page 277
7.5 Hydrogenation to Secondary and Tertiary Amines……Page 280
7.6.1 Aminonitriles……Page 283
7.6.2 Hydroxy- and Alkoxynitriles……Page 285
7.6.3 Hydrogenation Accompanied by Cyclization……Page 287
8.1.1 N-Unsubstituted Imines……Page 296
8.1.2 Aliphatic N-Substituted Imines……Page 297
8.1.3 Aromatic N-Substituted Imines……Page 298
8.2 Oximes……Page 300
8.2.1 Hydrogenation to Amines……Page 301
8.2.2 Hydrogenation to Hydroxylamines……Page 311
8.2.3 Hydrogenation Accompanied by Cyclization……Page 312
8.3.1 Hydrazones……Page 315
8.3.2 Azines……Page 320
9.2.1 Hydrogenation Kinetics……Page 325
9.2.2 Hydrogenation to Amines……Page 326
9.2.3 Hydrogenation to Nitroso or Hydroxyimino and Hydroxyamino Compounds……Page 332
9.2.4 Conjugated Nitroalkenes……Page 337
9.2.5 Hydrogenation Accompanied by Cyclization……Page 340
9.3.1 Hydrogenation to Amines……Page 342
9.3.2 Halonitrobenzenes……Page 352
9.3.3 Hydrogenation of Dinitrobenzenes to Aminonitrobenzenes……Page 357
9.3.4 Selective Hydrogenations in the Presence of Other Unsaturated Functions……Page 360
9.3.5 Hydrogenation Accompanied by Condensation or Cyclization……Page 363
9.3.6 Hydrogenation to Hydroxylamines……Page 369
9.3.7 Hydrogenation to Hydrazobenzenes……Page 372
9.4 Nitroso Compounds……Page 373
9.5 N-Oxides……Page 379
9.6.1 Azo Compounds……Page 381
9.6.2 Diazo Compounds……Page 385
9.6.3 Azides……Page 387
10.1.1 Hydrogenation to Alcohols……Page 397
10.1.2 Hydrogenation to Aldehydes……Page 401
10.2.1 Esters……Page 402
10.2.2 Hydrogenation of Unsaturated Esters to Unsaturated Alcohols……Page 408
10.2.4 Lactones……Page 409
10.2.5 Acid Anhydrides……Page 412
10.3 Acid Amides, Lactams, and Imides……Page 416
11.1 Aromatic Hydrocarbons……Page 424
11.1.1 Hydrogenation of Benzene to Cyclohexene……Page 429
11.1.2 Hydrogenation of Polyphenyl Compounds to Cyclohexylphenyl Derivatives……Page 431
11.1.3 Stereochemistry of Hydrogenation……Page 433
11.2.1 Phenols……Page 437
11.2.2 Hydrogenation to Cyclohexanones……Page 446
11.2.3 Phenyl Ethers……Page 451
11.3 Aromatic Compounds Containing Benzyl-Oxygen Linkages……Page 457
11.4 Carboxylic Acids and Esters……Page 464
11.5 Arylamines……Page 469
11.6 Naphthalene and Its Derivatives……Page 479
11.7 Anthracene, Phenathrene, and Related Compounds……Page 487
11.8 Other Polynuclear Compounds……Page 492
12.1.1 Pyrroles……Page 507
12.1.2 Indoles and Related Compounds……Page 510
12.1.3 Pyridines……Page 514
12.1.4 Quinolines, Isoquinolines, and Related Compounds……Page 528
12.1.5 Polynuclear Compounds Containing a Bridgehead Nitrogen……Page 542
12.1.6 Polynuclear Compounds with More than One Nitrogen Ring……Page 544
12.1.7 Compounds with More than One Nitrogen Atom in the Same Ring……Page 546
12.2.1 Furans and Related Compounds……Page 557
12.2.2 Pyrans, Pyrones, and Related Compounds……Page 564
12.3 S-Heterocycles……Page 572
13.1.1 Alcohols and Ethers……Page 582
13.1.2 Epoxy Compounds……Page 585
13.1.3 Benzyl-Oxygen Functions……Page 593
13.1.4 Stereochemistry of the Hydrogenolysis of Benzyl-Oxygen Compounds……Page 604
13.1.5 Vinyl-Oxygen Compounds……Page 608
13.2 Hydrogenolysis of Carbon-Nitrogen Bonds……Page 611
13.3 Hydrogenolysis of Organic Sulfur Compounds……Page 617
13.3.1 Thiols……Page 620
13.3.2 Thioethers……Page 623
13.3.3 Hemithioacetals……Page 624
13.3.4 Dithioacetals……Page 626
13.3.5 Thiophenes……Page 627
13.3.7 Disulfides……Page 628
13.3.8 Hydrogenolysis over Metal Sulfide Catalysts……Page 629
13.3.9 Sulfones, Sulfonic Acids, and Their Derivatives……Page 630
13.3.10 Stereochemistry of the Desulfurization with Raney Nickel……Page 632
13.4.1 R-X Bonds at Saturated Carbons……Page 633
13.4.2 Activated Alkyl and Cycloalkyl Halides……Page 639
13.4.3 Allyl and Vinyl Halides……Page 641
13.4.4 Benzyl and Aryl Halides……Page 643
13.4.5 Halothiazoles……Page 647
13.4.6 Hydrogenolysis of Acid Chlorides to Aldehydes (the Rosenmund Reduction)……Page 648
13.5.1 Cyclopropanes……Page 650
13.5.3 Open-Chain Carbon-Carbon Bonds……Page 657
13.6.1 Nitrogen-Oxygen and Nitrogen-Nitrogen Bonds……Page 661
13.6.2 Oxygen-Oxygen Bonds……Page 663
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