HANDBOOK OF HETEROGENEOUS CATALYTIC HYDROGENATION FOR ORGANIC SYNTHESIS SHIGEO NISHIMURA Professor Emeritus Tokyo University of Agriculture and Technology A Wiley-Interscience Publication JOHN WILEY & SONS, INC New York Chichester Weinheim Brisbane Singapore Toronto This book is printed on acid-free paper Copyright © 2001 by John Wiley & Sons, Inc All rights reserved Published simultaneously in Canada No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4744 Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, (212) 850-6011, fax (212) 850-6008, E-Mail: PERMREQ@WILEY.COM For ordering and customer service, call 1-800-CALL-WILEY Library of Congress Cataloging in Publication Data: Nishimura, Shigeo Handbook of heterogeneous catalytic hydrogenation for organic synthesis / Shigeo Nishimura p cm Includes bibliographical references and indexes ISBN 0-471-39698-2 (cloth : alk paper) Hydrogenation Catalysis Organic compounds—Synthesis I Title QD281.H8 N57 2001 547Y.23—dc21 Printed in the United States of America 10 00-043746 PREFACE Catalytic hydrogenation is undoubtedly the most useful and widely applicable method for the reduction of chemical substances, and has found numerous applications in organic synthesis in research laboratories and industrial processes Almost all catalytic hydrogenations have been accomplished using heterogeneous catalysts since the earliest stages Homogeneous catalysts have been further developed and have extended the scope of catalytic hydrogenation, in particular, for highly selective transformations However, heterogeneous catalysts today continue to have many advantages over homogeneous catalysts, such as in the stability of catalyst, ease of separation of product from catalyst, a wide range of applicable reaction conditions, and high catalytic ability for the hydrogenation of hard-to-reduce functional groups such as aromatic nuclei and sterically hindered unsaturations and for the hydrogenolyses of carbon– carbon bonds Also, many examples are included here where highly selective hydrogenations have been achieved over heterogeneous catalysts, typically in collaboration with effective additives, acids and bases, and solvents Examples of the hydrogenation of various functional groups and reaction pathways are illustrated in numerous equations and schemes in order to help the reader easily understand the reactions In general, the reactions labeled as equations are described with experimental details to enable the user to choose a pertinent catalyst in a proper ratio to the substrate, a suitable solvent, and suitable reaction conditions for hydrogenation to be completed within a reasonable time The reactions labeled as schemes will be helpful for better understanding reaction pathways as well as the selectivity of catalysts, although the difference between equations and schemes is not strict Simple reactions are sometimes described in equations without experimental details Comparable data are included in more than 100 tables, and will help the user understand the effects of various factors on the rate and/or selectivity, including the structure of compounds, the nature of catalysts and supports, and the nature of solvents and additives A considerable number of experimental results not yet published by the author and coworkers can be found in this Handbook This book is intended primarily to provide experimental guidelines for organic syntheses However, in fundamental hydrogenations, mechanistic aspects (to a limited extent) are also included The hydrogenations of industrial importance have been described with adequate experimental and mechanistic details The references quoted here are by no means comprehensive In general, those that seem to be related to basic or selective hydrogenations have been selected xi xii PREFACE I am grateful to the authors of many excellent books to which I have referred during preparation of this book These books are listed at the end of chapters under “General Bibliography.” I wish to express my thanks to the libraries and staff of The Institute of Physical and Chemical Research, Wako, Saitama and of Tokyo University of Pharmacy and Life Science, Hachioji, Tokyo I acknowledge John Wiley and Sons, Inc and their editorial staff for their cordial guidance and assistance in publishing this book I thank Professor Emeritus Michio Shiota of Ochanomizu University and Professor Yuzuru Takagi of Nihon University for their helpful discussions Special thanks are due to my three children who provided me with a new model personal computer with a TFT-LC display for preparing the manuscript and to my wife Yasuko, who had continuously encouraged and supported me in preparing and publishing this book until her death on November 28, 1999 SHIGEO NISHIMURA Hachioji, Tokyo CONTENTS Preface xi Hydrogenation Catalysts 1.1 Nickel Catalysts 1.1.1 1.1.2 1.1.3 1.1.4 1.1.5 1.2 1.3 1.4 1.5 1.6 1.7 Reduced Nickel Nickel from Nickel Formate Raney Nickel Urushibara Nickel Nickel Boride 19 20 Cobalt Catalysts 23 1.2.1 1.2.2 1.2.3 1.2.4 23 24 25 26 Reduced Cobalt Raney Cobalt Cobalt Boride Urushibara Cobalt Copper Catalysts Iron Catalysts Platinum Group Metal Catalysts 26 28 29 1.5.1 1.5.2 1.5.3 1.5.4 1.5.5 1.5.6 30 34 38 40 41 42 Platinum Palladium Ruthenium Rhodium Osmium Iridium Rhenium Catalysts The Oxide and Sulfide Catalysts of Transition Metals Other than Rhenium 42 43 Reactors and Reaction Conditions 52 2.1 2.2 Reactors Reaction Conditions 52 53 2.2.1 2.2.2 53 59 Inhibitors and Poisons Temperature and Hydrogen Pressure v vi CONTENTS Hydrogenation of Alkenes 64 3.1 3.2 3.3 3.4 3.5 3.6 Isolated Double Bonds: General Aspects Hydrogenation and Isomerization Alkyl-Substituted Ethylenes Selective Hydrogenation of Isolated Double Bonds Fatty Acid Esters and Glyceride Oils Conjugated Double Bonds 65 68 72 77 84 92 3.6.1 3.6.2 3.6.3 92 93 94 3.7 3.8 Aryl-Substituted Ethylenes α,β-Unsaturated Acids and Esters Conjugated Dienes Stereochemistry of the Hydrogenation of Carbon–Carbon Double Bonds 100 3.7.1 3.7.2 3.7.3 100 105 111 Syn and Apparent Anti Addition of Hydrogen Catalyst Hindrance Effects of Polar Groups Selective Hydrogenations in the Presence of Other Functional Groups 119 3.8.1 3.8.2 3.8.3 119 122 3.8.4 3.8.5 Isolated Double Bonds in the Presence of a Carbonyl Group Double Bonds Conjugated with a Carbonyl Group Stereochemistry of the Hydrogenation of ∆1,9-2-Octalone and Related Systems An Olefin Moiety in the Presence of Terminal Alkyne Function β-Alkoxy-α,β-Unsaturated Ketones (Vinylogous Esters) 129 136 137 Hydrogenation of Alkynes 148 4.1 4.2 4.3 149 160 165 Hydrogenation over Palladium Catalysts Hydrogenation over Nickel Catalysts Hydrogenation over Iron Catalysts Hydrogenation of Aldehydes and Ketones 170 5.1 5.2 5.3 Aldehydes Hydrogenation of Unsaturated Aldehydes to Unsaturated Alcohols Ketones 170 178 185 5.3.1 5.3.2 5.3.3 186 190 5.3.4 5.3.5 5.4 Aliphatic and Alicyclic Ketones Aromatic Ketones Hydrogenation Accompanied by Hydrogenolysis and Cyclization Amino Ketones Unsaturated Ketones 193 197 198 Stereochemistry of the Hydrogenation of Ketones 200 5.4.1 200 Hydrogenation of Cyclohexanones to Axial Alcohols CONTENTS 5.4.2 5.4.3 5.4.4 5.4.5 5.4.6 5.4.7 5.5 Hydrogenation of Cyclohexanones to Equatorial Alcohols Effects of a Polar Substituent and Heteroatoms in the Ring Alkylcyclopentanones Hindered Ketones Hydrogenation of Fructose Enantioselective Hydrogenations Mechanistic Aspects of the Hydrogenation of Ketones vii 205 207 208 209 212 212 218 Preparation of Amines by Reductive Alkylation 226 6.1 6.2 6.3 6.4 6.5 6.6 226 236 241 246 247 6.7 Reductive Alkylation of Ammonia with Carbonyl Compounds Reductive Alkylation of Primary Amines with Carbonyl Compounds Preparation of Tertiary Amines Reductive Alkylation of Amine Precursors Alkylation of Amines with Alcohols Synthesis of Optically Active α-Amino Acids from α-Oxo Acids by Asymmetric Transamination Asymmetric Synthesis of 2-Substituted Cyclohexylamines 248 250 Hydrogenation of Nitriles 254 7.1 7.2 7.3 7.4 7.5 7.6 General Aspects Hydrogenation to Primary Amines Hydrogenation of Dinitriles to Aminonitriles Hydrogenation to Aldimines or Aldehydes Hydrogenation to Secondary and Tertiary Amines Hydrogenation Accompanied by Side Reactions 254 259 265 267 270 273 7.6.1 7.6.2 7.6.3 273 275 277 Aminonitriles Hydroxy- and Alkoxynitriles Hydrogenation Accompanied by Cyclization Hydrogenation of Imines, Oximes, and Related Compounds 286 8.1 286 Imines 8.1.1 8.1.2 8.1.3 8.2 Oximes 8.2.1 8.2.2 8.2.3 8.3 N-Unsubstituted Imines Aliphatic N-Substituted Imines Aromatic N-Substituted Imines 286 287 288 290 Hydrogenation to Amines Hydrogenation to Hydroxylamines Hydrogenation Accompanied by Cyclization 291 301 302 Hydrazones and Azines 305 8.3.1 8.3.2 305 310 Hydrazones Azines viii CONTENTS Hydrogenation of Nitro, Nitroso, and Related Compounds 315 9.1 9.2 Hydrogenation of Nitro Compounds: General Aspects Aliphatic Nitro Compounds 315 315 9.2.1 9.2.2 9.2.3 315 316 9.2.4 9.2.5 9.3 322 327 330 Aromatic Nitro Compounds 332 9.3.1 9.3.2 9.3.3 9.3.4 Hydrogenation to Amines Halonitrobenzenes Hydrogenation of Dinitrobenzenes to Aminonitrobenzenes Selective Hydrogenations in the Presence of Other Unsaturated Functions Hydrogenation Accompanied by Condensation or Cyclization Hydrogenation to Hydroxylamines Hydrogenation to Hydrazobenzenes 332 342 347 Nitroso Compounds N-Oxides Other Nitrogen Functions Leading to the Formation of Amino Groups 363 369 371 9.6.1 9.6.2 9.6.3 371 375 377 9.3.5 9.3.6 9.3.7 9.4 9.5 9.6 Hydrogenation Kinetics Hydrogenation to Amines Hydrogenation to Nitroso or Hydroxyimino and Hydroxyamino Compounds Conjugated Nitroalkenes Hydrogenation Accompanied by Cyclization Azo Compounds Diazo Compounds Azides 350 353 359 362 10 Hydrogenation of Carboxylic Acids, Esters, and Related Compounds 387 10.1 Carboxylic Acids 387 10.1.1 Hydrogenation to Alcohols 10.1.2 Hydrogenation to Aldehydes 10.2 Esters, Lactones, and Acid Anhydrides 10.2.1 10.2.2 10.2.3 10.2.4 10.2.5 Esters Hydrogenation of Unsaturated Esters to Unsaturated Alcohols Hydrogenation of Esters to Ethers Lactones Acid Anhydrides 387 391 392 392 398 399 399 402 10.3 Acid Amides, Lactams, and Imides 406 11 Hydrogenation of Aromatic Compounds 414 11.1 Aromatic Hydrocarbons 414 CONTENTS 11.1.1 Hydrogenation of Benzene to Cyclohexene 11.1.2 Hydrogenation of Polyphenyl Compounds to Cyclohexylphenyl Derivatives 11.1.3 Stereochemistry of Hydrogenation 11.2 Phenols and Phenyl Ethers 11.3 11.4 11.5 11.6 11.7 11.8 ix 419 421 423 427 11.2.1 Phenols 11.2.2 Hydrogenation to Cyclohexanones 11.2.3 Phenyl Ethers 427 436 441 Aromatic Compounds Containing Benzyl–Oxygen Linkages Carboxylic Acids and Esters Arylamines Naphthalene and Its Derivatives Anthracene, Phenathrene, and Related Compounds Other Polynuclear Compounds 447 454 459 469 477 482 12 Hydrogenation of Heterocyclic Aromatic Compounds 497 12.1 N-Heterocycles 497 12.1.1 12.1.2 12.1.3 12.1.4 12.1.5 12.1.6 12.1.7 Pyrroles Indoles and Related Compounds Pyridines Quinolines, Isoquinolines, and Related Compounds Polynuclear Compounds Containing a Bridgehead Nitrogen Polynuclear Compounds with More than One Nitrogen Ring Compounds with More than One Nitrogen Atom in the Same Ring 12.2 O-Heterocycles 12.2.1 Furans and Related Compounds 12.2.2 Pyrans, Pyrones, and Related Compounds 497 500 504 518 532 534 536 547 547 554 12.3 S-Heterocycles 562 13 Hydrogenolysis 572 13.1 Hydrogenolysis of Carbon–Oxygen Bonds 572 13.1.1 13.1.2 13.1.3 13.1.4 Alcohols and Ethers Epoxy Compounds Benzyl–Oxygen Functions Stereochemistry of the Hydrogenolysis of Benzyl–Oxygen Compounds 13.1.5 Vinyl–Oxygen Compounds 13.2 Hydrogenolysis of Carbon–Nitrogen Bonds 13.3 Hydrogenolysis of Organic Sulfur Compounds 13.3.1 Thiols 572 575 583 594 598 601 607 610 x CONTENTS 13.3.2 Thioethers 13.3.3 Hemithioacetals 13.3.4 Dithioacetals 13.3.5 Thiophenes 13.3.6 Thiol Esters and Thioamides 13.3.7 Disulfides 13.3.8 Hydrogenolysis over Metal Sulfide Catalysts 13.3.9 Sulfones, Sulfonic Acids, and Their Derivatives 13.3.10 Stereochemistry of the Desulfurization with Raney Nickel 13.4 Hydrogenolysis of Carbon–Halogen Bonds 13.4.1 R–X Bonds at Saturated Carbons 13.4.2 Activated Alkyl and Cycloalkyl Halides 13.4.3 Allyl and Vinyl Halides 13.4.4 Benzyl and Aryl Halides 13.4.5 Halothiazoles 13.4.6 Hydrogenolysis of Acid Chlorides to Aldehydes (the Rosenmund Reduction) 13.5 Hydrogenolysis of Carbon–Carbon Bonds 13.5.1 Cyclopropanes 13.5.2 Cyclobutanes 13.5.3 Open-Chain Carbon–Carbon Bonds 13.6 Miscellaneous Hydrogenolyses 13.6.1 Nitrogen–Oxygen and Nitrogen–Nitrogen Bonds 13.6.2 Oxygen–Oxygen Bonds 613 614 616 617 618 618 619 620 622 623 623 629 631 633 637 638 640 640 647 647 651 651 653 General Bibliography 664 Author Index 665 Subject Index 693 723 Index Terms Links O-Methylacetoxime Methylacetylene 2-Methylaminopyridine O-Methylbenzaldoxime 2-Methylbenzimidazole 4-Methylbutyrophenone 9-Methylcarbazole 2-Methylchromanone 2-Methylchromone α-Methylcinnamaldehyde 3-Methylcrotonaldehyde α-Methylcrotonaldehyde 4-(4-Methylcyclohex-1-enyl)but-3-yn-2-one (compound 16) 1-Methylcyclohexanecarbonyl chloride (eq.13.139) 2-Methylcyclohexanone oxime 3-Methylcyclohexanone oxime 2-Methylcyclohexanone 2-Methylcyclohexanone cyanohydrin 3-Methylcyclohexanone 4-Methylcyclohexanone Methylcyclohexenes, 3- and 4effect of solvents on isomerization 2-Methylcyclopentanone 3-Methylcyclopentanone 2-Methylcyclopentylidenecyclopentane Methylcyclopropane 2-Methyldehydroquinolizinium iodide N-Methyldibenzylamines effect of para substituents on hydrogenolysis 5-Methylene-1,3-dioxanes 2-substituted 2-t-butyl Methylenecyclohexane effect of solvents on isomerization 3,4-Methylenedioxy-β-nitrostyrene β-(3,4-Methylenedioxyphenyl)-γ-nitrobutyrophenone (compound 14) 3,4-Methylenedioxyphenylacetonitrile 2-Methylenenorbornane 3,3-dimethyl5-Methylenenorbornene 5-Methylenetetrahydropyran 2-t-butyl2-Methylfuran in acetone and aqueous hydrogen chloride in presence of water 2-Methylharman 302 148 514 302 538 191 502 557 557 183 179 183 159 639 299 299 232 276 204 189 232 70 208 210 105 641 533 180 300 190 201 210 106 601 602 114 114 115 115 70 329 330 330 261 109 109 78 114 547 548 548 535 115 548 This page has been reformatted by Knovel to provide easier navigation 550 202 206 724 Index Terms Links 2-Methylindazole 2-Methylindole 1-Methylindole 3-Methylindole 1-{β-[3-(2-Methylindolyl)]ethyl}-3-acetylpyridinium bromide (compound 18a) 2-Methylmethylenecyclohexane 2-Methylmethylenecyclopentane 2-Methylnaphthalene 2-Methylpentane-2,4-diol 2-Methylphenanthroline 2-Methylpyrazine 2-Methylpyrimidine 4-Methylpyrimidine Methylpyrimidines,2-,4-, and 52-Methylquinoline 2-Methyltetrahydrofuran 2-Methylyobyrinium iodide 2-Methoxycyclohexanone 4-Methoxycyclohexanone Molybdenum oxides Molybdenum sulfides Monochloroacetic acid β-Morpholinopropionitrile 4-Morpholinopyridine Myrtenic acid Myrtenol Naphthalene rate of hydrogenation Naphthalenes 1-alkyl-substituted Naphthalene-1-sulfonyl chloride (eq 13.101) Naphthalene-2-sulfonic acid 2-Naphthalenecarbaldehyde 1-Naphthol 2-Naphthol Naphthols α-Naphthonitrile β-Naphthonitrile 2-Naphthoyl chloride 2-(2-Naphthoyloxy)pyridine 2'-Naphthyl-1-thio-β-D-ribopyranoside tribenzoate Naphthylidenemenaphthylamines Ni-kieselguhr effect of promoters reduction time and temperature and activity 537 500 503 500 516 68 104 470 649 535 544 542 542 542 522 550 534 207 207 43 43 629 274 515 110 110 12 469 470 621 621 176 471 471 476 471 259 259 639 511 614 289 105 106 275 417 470 177 473 472 477 472 This page has been reformatted by Knovel to provide easier navigation 474 473 474 475 725 Index Terms Links with ammonium carbonate Ni-Al2O3 activation with KBH4 Nickel boride P-1 P-2 on SiO2 P-2 by Paul et al colloidal Nickel catalysts Nickel from nickel formate by Allisson et al by Sasa by Wurster Nicotinamide Nicotinic acid (pyridine-3-carboxylic acid) 2-Nitro 1,3-glycols 2-Nitro alcohols decomposition of γ-Nitro ketones hydrogenation to pyrrolidines γ-Nitro phenyl ketones 2-Nitro-(or 2-amino)-4,5-dimethoxyphenylacetonitrile 2-Nitro-1,3-propanediol 2-Nitro-1-(4-pyridyl)ethanol 2-Nitro-1-alkanols 2-Nitro-1-butene (1-Nitro-1-cyclohexyl) (4-pyridyl)methanol 1-Nitro-1-octadecene 2-Nitro-1-phenyl-1-propanol 2-Nitro-2'-carboxybiphenyl (and carboxy derivatives) 2-Nitro-2'-cyanobiphenyl 1-Nitro-2-butanol 2-Nitro-2-methyl-1-propanol 4-Nitro-2-methyl-3-butanol 5-Nitro-2-methyl-4-pentanol 1-Nitro-2-octanol 1-Nitro-2-pentanol 1-Nitro-2-propanol 1-Nitro-2-thiocyanatobenzene N-(2-Nitro-5-methylphenyl)-dl-α-alanine (eq 9.68) γ-Nitro-β-phenyl-2-pentanone (compound 13) 2-Nitro-p-cymene (eq 9.35) m-Nitroacetophenone (eq 9.36) Nitroalkanes hydrogenation to amines of C1 to C4 5 20 22 22 22 21 22 2–23 515 507 318 318 319 330 331 331 277 319 319 319 327 319 328 320 354 354 323 318 323 323 323 323 323 355 358 330 334 334 316 321 316 508 320 278 320 320 329 355 355 319 317 322 This page has been reformatted by Knovel to provide easier navigation 318 319 320 726 Index Terms Links rate of hydrogenation o-Nitroanisole p-Nitroanisole m-Nitrobenzalacetone m-Nitrobenzalacetophenone Nitrobenzene heat of hydrogenation hydrogenation to phenylhydroxylamine rate of hydrogenation rates for p-substituted nitrobenzenes p-Nitrobenzoyl chloride S-(p-Nitrobenzyloxycarbonyl)cysteine (eq.13.30) Nitrocinnamic acids and esters Nitrocyclododecane Nitrocyclohexane 4-Nitrocyclohexenes 1-Nitrocyclooctene 2-Nitroethanol Nitroguanidine hydrogenation to aminoguadinine hydrogenation to nitrosoguanidine 5-Nitroisoquinoline Nitromethane 1-(Nitromethyl)cyclohexanol endo-5-Nitronorbornene o-Nitrophenol p-Nitrophenol cis-2-(o-Nitrophenyl)-1,2,5,6-tetrahydrobenzoic acid (eq 9.67) o-Nitrophenylacetone p-Nitrophenylacetonitrile (eq 7.45) hydrogenation in presence of dimethylamine 3-Nitrophenylacetylene o-Nitrophenylglycine Nitrophthalic acids, 3- and 44-Nitropyrogallol 4-Nitrosalicylic acid N-Nitrosamines 9-Nitroso-10-chlorodecalin 1-Nitroso-4-methyl-4-benzylpiperazinium chloride (eq 9.72) N-Nitroso-N-butyl-p-anisidine N-Nitroso-N-ethylphenylamine Nitrosobenzene Nitrosocyclododecane dimer Nitrosocyclohexane dimer N-Nitrosodialkylamines N-Nitrosodicyclohexylamine N-Nitrosodiethanolamine N-Nitrosodiisopropylamine 315 339 359 350 350 333 333 359 336 336 640 591 350 325 323 317 328 323 323 322 338 323 320 317 335 335 358 357 271 35 356 339 337 339 364 363 365 365 364 364 326 326 366 368 368 368 316 340 334 336 360 361 351 326 324 327 325 326 366 367 337 341 329 339 321 336 358 353 365 327 327 This page has been reformatted by Knovel to provide easier navigation 368 727 Index Terms Links N-Nitrosodimethylamine N-Nitrosodiphenylamine N-Nitrosodipropylamine N-Nitrosodiisobutylamine N-Nitrosomorpholine N-Nitrosopiperidine Nitrostilbene(s) 4α3-Nitrostyrene b-Nitrostyrene(s) o-Nitrotoluene (eq 9.37) hydrogenation to hydrazotoluene Nonanal Nonanoic acid 2-Nonanone 5-Nonanone 19-Nor-3-oxo-4-ene steroids rate of hydrogenation 19-Norandrost-4-ene-3,17-dione Norcamphor A-Nortestosterone 366 364 365 368 368 364 351 351 330 351 327 334 363 228 389 231 230 131 133 131 212 136 Octadecane-1,12-diol 1-Octadecyne 2-Octadecyne 9-Octadecyne 11-Octadecynoic acid cis-as-Octahydro-9-phenanthrol Octahydrocoumarin ∆1,9-Octalin stereochemistry of hydrogenation ∆9,10-Octalin ∆1,9-2-Octalone 10-ethoxycarbonyleffect of angular substituents stereochemistry of hydrogenation Octanoic acid, see Caprylic acid 1-Octene isomerization to hydrogenation ratio Octyl caprylate equilibria with octanol and hydrogen 1-Octyne 2-Octyne 3-Octynoic acid 4-Octynoic acid 5-Octynoic acid 6-Octynoic acid 649 161 161 161 161 481 400 77 103 77 129 129 129 129 367 365 328 341 329 360 229 230 232 134 162 401 78 78 130 130 130 72 69 392 154 161 162 162 161 162 393 165 This page has been reformatted by Knovel to provide easier navigation 135 728 Index Terms Links Oleates Oleic acid ∆16-20-One steroids Osmium black Osmium catalysts 2-Oxa-7,7-dichlorobicyclo[4.1.0]heptane 7-Oxabicyclo[2.2.1]hept-2-ene-2,3-dicarboxylic acids Oxalic acid Oxide and sulfide catalysts other than rhenium N-Oxides Oximes of alicyclic ketones β-Oxo esters, see β-Keto esters ∆4-3-Oxo steroid benzylthioenol ethers 17-Oxo steroid enol acetates 2-Oxo-1-oxadecalin 1-Oxo-3-methyl-2-tetralylacetic acid (compound 31) 3-Oxo-4-oxa-5a-cholestane 7-Oxocholesteryl acetate 3-Oxo-∆1,4 steroids 3-Oxo-∆4 steroids effects of 17-substituents effects of substituents at C11, C17, and C20 rate of hydrogenation 3-Oxo-∆4,6 steroid thioenol ether Ozonides hydrogenolysis to aldehydes and ketones Palladium black by Zelinsky and Glinka from palladium hydroxide Palladium catalysts effects of oxide supports Palladium oxide (by Shriner and Adams) Pd-CaCO3 lead-poisoned (Lindlar catalyst) Pd(OH)2-C (by Pearlman) (20% Pd) Pd-BaSO4 (5% Pd) (procedure A by Mozingo) Pd-C (10% Pd) (procedure D by Mozingo) 36 Pd-C (5% Pd) (procedure B by Mozingo) Pd-C (5% Pd) (procedure C by Mozingo) Pelargoaldehyde (nonanal) Pentachlorocyclopentadiene Pentachlorophenol Pentadecanedioic acid 2,4-Pentadienal Pentamethylbenzene rate of hydrogenation 3-Pentanone oxime 84 391 130 42 41 628 113 389 43 369 370 371 299 612 599 402 585 402 123 128 130 133 131 133 612 613 130 135 132 134 613 133 135 35 36 653 34 34 34 38 35 37 37 35 36 36 227 631 428 389 122 415 294 419 299 This page has been reformatted by Knovel to provide easier navigation 37 38 729 Index Terms Links Pentaphenylethane 1-Pentene isomerization to hydrogenation ratio p-(2-Pentyl)aniline Perfluoro-2-nitropropane (compound 85) Phenanthrene Phenanthridine 9-Phenanthrol 1,10-Phenanthroline 4,7-Phenanthroline Phenanthrolines Phenol benzyl ethers Phenol hydrogenation to cyclohexanone rate of hydrogenation Phenolic acids Phenols extents of hydrogenolysis hydrogenation to cyclohexanones rate constants Phenyl 1-thio-β-cellobioside heptaacetate Phenyl ether, see Diphenyl ether Phenyl ethers Phenyl phosphates in glucose phosphates synthesis (eq 13.52) 2-Phenyl-1,2-propanediol 4-Phenyl-1,3-dioxolanes 2-Phenyl-1-butanol (eq 11.45) 3-Phenyl-1-butanol (eq 11.46) 3-Phenyl-1-butene 3-Phenyl-1-propanol 1-Phenyl-1-propyne 2-Phenyl-2,3-dihydro-4H-pyran 4-Phenyl-2-oxobutyric acid 1-Phenyl-3-(cyclohex-1-enyl)-2-propynone (compound 21) 1-Phenyl-4-penten-3-yn-1-one Phenyl-α,ω-glycols N-Phenyl-p-phenylenediamine alkylation with 4-methyl-2-pentanone N-Phenylacetamide Phenylacetic acid Phenylacetic esters Phenylacetone hydrazone Phenylacetonitrile hydrogenation to aldehyde hydrogenation to give semicarbazone Phenylacetylene 647 70 460 631 478 531 481 536 535 535 589 427 439 13 428 427–441 429 436 429 614 441 446 600 600 650 586 454 454 73 651 151 555 217 160 160 449 241 408 390 397 305 255 267 268 152 479 480 481 536 536 429 436 430 437 430 615 435 438 436 439 440 442 447 443 444 445 152 154 161 164 306 256 268 307 259 260 264 154 155 161 74 This page has been reformatted by Knovel to provide easier navigation 730 Index Terms Links 2-Phenylalkylamines 3-Phenylazo-2,6-dihydroxy-4-pyridinecarboxylic acid (and methyl ester) (eq 9.82) 3-Phenylazo-2,6-dihydroxybenzamide (eq 9.80) 2-Phenylazo-4,5-dimethylphenol (eq 9.81) p-Phenylazoaniline rate of hydrogenation 2-Phenylbenzimidazole 1-Phenylbicyclo[4.1.0]heptane 4-Phenylcinnoline 2-Phenylcyclohexanone oxime Phenylcyclopropane o-Phenylenediacetonitrile 2-(2-Phenylethyl)pyridine Phenylethylene (styrene) 2-Phenylfuran Phenylmethylacetylene, see 1-Phenyl-1-propyne 4-Phenylphenol benzyl ethers 4-Phenylphenol 3-Phenylphthalidylnitromethane Phenylpropargyl alcohol Phenylpropiolic acid 4-(3-Phenylpropyl)pyridine 1-Phenylpyrazole 4-Phenylpyridine N-Phenylpyridinium chloride 1-Phenylpyrrole 4-Phenylthiohydantoin Phosphoric acid benzyl esters Phthalazine Phthalic anhydride 3- and 4-dimethylamino3- or 4-substituted 4-methoxyPhthalic dichlorides, m- and p3-Phthalidylnitromethanes Phthalimide(s) N-ethoxycarbonyl (eq 10.51) N-pentyl (eqs 10.45 and 10.49) N-substituted Phthalonitrile o-Phthalonitrile, see Phthalonitrile Phthaloyl dichloride Pinacolone (3,3-dimethyl-2-butanone) (eqs 5.29 and 5.30) α-Pinene β-Pinene α-Piperidinocaprylonitrile α-Piperidinophenylacetonitrile 460 373 373 373 372 538 644 541 300 642 279 506 92 548 589 434 322 157 149 510 536 510 508 497 610 586 541 402 404 404 404 640 321 409 410 409 410 263 640 187 109 109 274 274 645 93 498 611 587 403 322 411 278 110 This page has been reformatted by Knovel to provide easier navigation 404 731 Index Terms Links 2-Piperidone N-(2-cyclohexylethyl)-4-methyl- (eq 10.46) 1-(N-Piperidyl)-2,4-dinitrobenzene 2-(Piperonylideneamino)indane Platinum catalysts Platinum group metal catalysts Platinum metal sulfides Platinum oxide (by Adams et al.) Platunum blacks by Feulgen Polynuclear aromatic hydrocarbons 5α-Pregnane-3,20-dione Propiomesitylene Propionic anhydride Propionitrile Propiophenone Pt-C (by Kaffer) Pt-SiO2 Pteridines Pterin (2-amino-4-oxo-3,4-dihydropteridine) 2-(Purin-6-ylamino)ethyl disulfide (eq 13.95) 2-(Purin-8-ylamino)ethyl disulfide (disulfide from compound 64) Purine hydrochloride Purine Pyran-2,6-dicarboxylic acid Pyrans Pyrazoles 2-Pyrazolines Pyrene Pyridazine Pyridine hydrochloride Pyridine N-oxide(s) Pyridine N-alkylation Pyridineacrylic ester, amide, and acid, 3- and 4N-oxides of Pyridines 2-substituted (compounds 9a–9d) hydrogenation to tetrahydropyridines with basic side chains Pyrido-as-triazines Pyridocoline, see Quinolizine 2-(2-Pyridyl)ethanol Pyrimidine N-oxide Pyrimidine 2-(2-Pyrimidinylamino)ethyl disulfide (disulfide from compound 65) Pyrogallol 409 350 290 30 29–42 44 32 30 31 477–488 202 191 403 258 192 33 34 545 546 619 618 545 545 555 554 536 537 482 540 508 369 505 506 370 504–518 509 515 508 541 31 33 31 263 619 555 537 538 483 370 507 507 510 516 650 370 542 618 431 32 619 This page has been reformatted by Knovel to provide easier navigation 371 517 518 34 732 Index Terms Links 4-Pyrone 4-Pyrone-2-carboxylic acid, see Comanic acid 2-Pyrones (coumalins) 4-Pyrones Pyrrocoline, see Indolizine Pyrrole N-substituted Pyrroles 2-Pyrrolidones N-pentyl (eq 10.44) 556 557 559 556 557 497 497 497 498 Quaternary 3-hydroxypyridium chlorides Quaternary pyridinium chlorides Quercetin Quinazoline Quinoline N-oxide Quinoline (s) selectivity to tetrahydro derivatives 512 508 559 542 370 518 521 526 528 264 638 533 533 534 544 hydrogenation to dihydro derivatives Quinoline-4-carbonitrile (eq 7.34) Quinoline-S Quinolizine (pyridocoline) Quinolizinium iodide Quinolizones Quinoxaline D-Ramnose hydrate Raney cobalt by Aller from Co2Al9 Raney Cu Raney Fe Raney nickel activation by other metals N-4 Platinized T-4 W-1–W-7 W-2 W-6 (and also W-5 and W-7) degree of leaching and activity from NiAl3 optimal degrees of leaching Rapeseed oil Reduced cobalt Reduced Cu (by Ipatieff et al.) Reduced nickel 499 408 172 24 25 25 28 28 7–19 15 10 17 8 13 14 11 15 13 88 23 27 543 519 522 527 520 523 528 524 525 17 18 19 545 25 16 15 18 14 19 12 89 24 This page has been reformatted by Knovel to provide easier navigation 733 Index Terms Links Reductive dehydroxymethylation Resorcinol hydrogenation to cyclohexane-1,3-dione Rh-Pt oxide, 7:3 (Nishimura catalyst) Rh black Rh(OH)3 (10% Rh)-Pd(OH)2 (0.1% Pd)-C Rh(OH)3 Rhenium black Rhenium catalysts Rhenium selenides Rhenium sulfides Rhodium catalysts α-D-Ribofuranose 1,5-diphosphate dibenzyl diphenyl ester 2,3-cyclic carbonate (eq.13.25) D-Ribose reactions leading to hexitylamines Rosenmund reduction Ru(OH)3 (10% Ru)-Pd(OH)2 (0.1% Pd)-C Ruthenium black from ruthenium hydroxide Ruthenium catalysts Ruthenium dioxide (by Pichler) Ruthenium hydroxide Salicylaldehyde Sebaconitrile Simmons-Smith reaction Sodium itaconate rate of hydrogenation Sodium p-nitrophenoxide rate of hydrogenation Soybean oil Spiro[cyclopropane-1,2'-adamantane] (eq.13.149) Spiro-(5-benzhydryl-1,3-oxathiolane-2,3'-cholestane) Stearic acid Stearolic acid Stearonitrile Stereochemistry of hydrogenation of ∆1,9-2-octalone and related systems of armatic hydrocarbons of carbon-carbon double bonds of isomeric xylenes of ketones of phenathrene effects of polar groups 649 429 441 40 40 40 40 43 42 43 43 40 430 433 573 43 41 587 321 638 40 40 38 39 39 639 640 39 40 86 88 89 90 130 135 424 131 136 425 132 133 424 425 424 112 117 113 118 176 260 645 17 17 85 91 646 615 397 150 263 129 134 423 100–119 423 200–212 423 111 116 162 272 This page has been reformatted by Knovel to provide easier navigation 426 114 119 115 131 734 Index Terms Links Stereochemistry of hydrogenolysis of benzyl-oxygen compounds of carbon-nitrogen bonds of optically active 2-methyl-2-phenylaziridine ∆5 Steroids 19-hydroxy 3α,19-dihydroxy 3α-acetoxy,19-hydroxy 3β-substituted effects of 3α substituents ∆5,7 Steroids hydrogenation to ∆5-steroids Stilbene Styrene oxide 2-Styrylpyridine N-oxide 4-Styrylpyridine N-oxide 2-Styrylquinoline N-oxide 4-Styrylquinoline N-oxide N-Substituted benzylideneamines N-Substituted imines aliphatic N-alkylaldimines aliphatic aromatic 1-Substituted pyridinium salts with unsaturated group in 3-position (compounds 18a–18k) Succinamide Succinic acid (eq 10.2) Succinic anhydride substituted Diels-Alder adducts (compounds 8,12–14) Succinimides N-(2-cyclohexylethyl) N-β-phenethyl N-pentyl (eq 10.45) N-substituted Succinonitrile Succinyl dichloride Sugar alcohols manufacture of Sulfones Sulfonic acids Sulfoxides 16-Sulfoxidobenzyl-5-pregnen-3b-ol-20-one 3acetate (compound 67) Supported catalysts Supported platinum effects of oxide supports 132 133 207 208 594 603 606 595 605 607 596 606 597 607 118 118 118 110 110 119 119 119 98 92 583 369 370 371 371 290 99 93 287 287 288 516 406 389 402 403 403 410 409 409 409 265 640 173 620 620 622 111 370 371 288 289 290 517 407 390 403 404 405 278 279 404 410 266 621 622 33 33 This page has been reformatted by Knovel to provide easier navigation 209 735 Index Terms Links Supporting materials (supports or carriers) Supports, see Supporting materials Synergistic effects in platinum metal catalysts Tall oil 12,5,6-Tetrahydrophthalaldehyde Terephthalic acid Terephthalonitrile hydrogenation to 4-cyanobenzylamine Tertiary amines from secondary amines and carbonyl compounds from diarylamine and ketones Testosterone Tetraacetyl-1-bromo-1-deoxy-scyllo-quercitol (eq 13.110) Tetraalkylbutynediol 1,2,3,4-Tetrachloro-7,7-dimethoxynorbronene 1,2,3,4-Tetrachloronorbornene Tetrachloropentadiene cis,trans,cis-1,2,3,4-Tetracyanocyclobutane (eq.7.66) 5,6,7,8-Tetrahydro-2-quinoxalone 1,2,3,4-Tetrahydroacridine 1,2,3,4-Tetrahydrobenzo[f]quinoline 1,2,3,4-Tetrahydrocarbazoles 1,1a,4,4a-Tetrahydrofluoren-9-one cis-8-methyl-1amethoxycarbonylmethyl-(eq 3.47) Tetrahydrofluorene derivative (compound 95) effect of substituents Tetrahydrofurfuryl alcohol Tetrahydroindanones 1,2,3,4-Tetrahydrophenanthrene 3,4,5,6-Tetrahydrophthalimide Tetrahydroquinoxaline Tetrahydroxyquinone Tetralin ac-2-Tetralol ar-2-Tetralol 2-Tetralone oxime(s) Tetramethyl-1,3-cyclobutanedione 2,3,5,6-Tetramethylpyrazine 1,1,2-Tetraphenylethane 1,1,2,2-Tetraphenylethane Tetraphenylethylene 3-Thiabicyclo[3.2.1]octane (compound 61) 5-(2-Thienyl)valeric acid Thiochromones 2-substituted δ,δ'-Thiodivaleric acid 30 89 120 454 262 267 242 245 124 625 149 632 632 631 280 545 530 531 504 456 263 243 130 505 120 118 550 135 479 410 544 431 469 474 474 292 196 544 647 647 92 613 562 119 551 480 481 545 470 475 475 301 648 93 129 608 This page has been reformatted by Knovel to provide easier navigation 476 476 477 477 736 Index Terms Links Thionaphthol Thiophene 1,1-dioxide Thiophene Thiophene-2-carboxaldehyde Thymol Tolan see Diphenylacetylene Toluene rate of hydrogenation Toluenediamine, 2,4- and 2,6p-Toluenesulfonic acid derivatives p-Toluenesulfonyl chloride m-Toluic acid o-Toluic acid o-Toluidine m-Tolunitrile o-Tolunitrile p-Tolunitrile Tribenzylamine Trichloroacetic acid 4-Trichloromethyl-4-methylcyclohexanone Tricyclo[4.4.1.0]undecane (eq 150) Tridecanenitrile (eq.7.31) Tridehydro[18]annulene Triethylamine from acetaldehyde and ammona from ethylamine and acetaldehyde 2-Trifluoro-1-fluoro-1-nitroethane (compound 84) Trifluoroacetic acid Trifluoromethylbenzoic acids p-Trifluoromethylbenzonitrile (eq 7.32) β,β,4-Trifluorostyrene (compound 92) Trilinolein 3,4,5-Trimethoxybenzoyl chloride 1,2,4-Trimethyl-5-nitrocyclohexene 3,3,5-Trimethylcyclohexanone (dihydroisophorone) 1,1,2-Trimethylcyclopropane 2,4,6-Trimethylpyridine 2,4,6-Trimethylpyrimidine 4-(Trimethylsilyl)phenoxytrimethylsilane Trinonylamine from nonanal and ammonia Triphenylamine 1,1,2-Triphenylethylene Triphenylmethane Tripropylamine from propionaldehyde and ammona Tris(phenylazo)phloroglucinol Trisodiumtris(p-sulfonatophenylazo)phloroglucinol 610 563 562 562 440 414 21 465 620 620 454 454 461 259 259 256 601 623 627 646 264 155 241 242 631 390 634 264 633 88 639 317 206 641 507 542 574 241 469 92 414 620 563 441 415 61 418 415 621 259 263 629 391 242 415 241 374 374 This page has been reformatted by Knovel to provide easier navigation 416 419 417 648 419 737 Index Terms Links Tropinone cyanohydrin Tropinone oxime Ultrasonic irradiation 4-Undecene, cis- and trans4-Undecyne α,β-Unsaturated aldehydes hydrogenation to unsaturated alcohols Unsaturated fatty acids (and esters) hydrogenation to unsaturated alcohols Unsaturated ketone (s) compound 61,107 hydrogenation to unsaturated alcohols N-Unsubstituted imines Urushibara Cobalt Urushibara Fe Urushibara nickel U-Ni-B U-Ni-A Valeraldehyde γ-Valerolactone γ-alkylγ-butylValeronitrile hydrogenation in presence of butylamine Vanillin (4-hydroxy-3-methoxybenzaldehyde) (eq 5.14) Vinyl esters Vinyl ethers (enol ethers) 4-Vinylcyclohexene Vinylcyclopropane von Auwers-Skita-Barton rule (ASB rule) 276 300 52 68 150 179 184 151 180 181 182 257 259 272 599 599 600 600 391 198 286 26 28 19 19 19 172 399 399 400 256 271 176 598 598 199 400 642 200 643 m-Xylene rate of hydrogenation stereochemistry of hydrogenation o-Xylene rate of hydrogenation stereochemistry of hydrogenation p-Xylene stereochemistry of hydrogenation Xylenes rate of hydrogenation stereochemistry of hydrogenation 415 425 419 21 424 648 425 418 414 423 419 Yobyrine [1-(o-methylbenzyl)-β-carboline] 534 415 425 415 424 This page has been reformatted by Knovel to provide easier navigation 417 425 183 ... PERMREQ@WILEY.COM For ordering and customer service, call 1-800-CALL-WILEY Library of Congress Cataloging in Publication Data: Nishimura, Shigeo Handbook of heterogeneous catalytic hydrogenation for organic synthesis. .. order of the addition of the reagents The effect of time and temperature on the extent of reduction and catalytic HYDROGENATION CATALYSTS TABLE 1.2 Effect of Time and Temperature upon Extent of. .. g of catalytic metal; (b) hydrogenation of naphthalene (3 g) to tetrahydronaphthalene in cyclohexane (10 ml) at 60°C and 8.5 ± 1.5 MPa H2 over 0.08 g of catalytic metal; (c) hydrogenation of