Table Of ContentOXYGENATES BY HOMOLOGATION OR CO HYDROGENATION
WITH METAL COMPLEXES
Catalysis by Metal Complexes
VOLUME 16
Editors:
R. UGO, University of Milan, Milan, Italy
B. R. JAMES, The University of British Columbia, Vancouver, Canada
Advisory Board:
J. L. GARNEIT, The University ofN ew South Wales, Kensington, N.S.W., Australia
S. D. IITEL, E.I. du Pont de Nerrwurs Co., Inc., Wilmington, Del., U.S.A.
P. W. N. M. VAN LEEUWEN, Royal Shell Laboratory, Amsterdam, The Netherlands
L. MARKO, Hungarian Academy of Sciences, Veszprem, Hungary
A. NAKAMURA, Osaka University, Osaka, Japan
W. H. ORME-JOHNSON, M1.T., Cambridge, Mass., U.S.A.
R. L. RICHARDS, The University of Sussex at Falmer, Brighton, U.K.
A. YAMAMOTO, Tokyo Institute ofT echnology, Yokohama, Japan
The titles published in this series are listed at the end oft his volume.
OXYGENATES BY HOMOLOGATION
OR CO HYDROGENATION
WITH METAL COMPLEXES
Edited by
GIUSEPPE BRACA
University of Pisa, Italy
SPRINGER SCIENCE+BUSINESS MEDIA, B.V.
Library of Congress Cataloging-in-Publication Data
Oxygenates by homologation ar CO hydrogenation with metal complexes I
edited by Giuseppe Braca.
p. cm. -- ICatalysis by metal complexes ; v. 161
ISBN 978-94-010-4378-6 ISBN 978-94-011-0874-4 (eBook)
DOI 10.1007/978-94-011-0874-4
1. Alcahals--Synthesis. 2. Glycals--Synthesis. 3. Hydrogenatian.
4. Carbon monoxide. 5. Metal camplexes. 6. Catalysis. I. Braca,
Giuseppe, 1937- II. Series.
Q0305.A4098 1994
547'.0310459--dc20 93-23650
ISBN 978-94-010-4378-6
Printed on acid-free paper
All Rights Reserved
© 1994 Springer Science+Business Media Dordrecht
Originally published by Kluwer Academic Publishers in 1994
Softcover reprint ofthe hardcover Ist edition 1994
No part of the material protected by this copyright notice may be reproduced or
utilized in any form or by any means, electronic or mechanical,
inc1uding photocopying, recording or by any information storage and
retrieval system, without written permission fram the copyright owner.
CONTENTS OF VOLUME
Monoalcohols, Glycols and their Ethers and Esters by CO Hydrogenation
G. Braca, A. M Raspolli Galletti and G. Shrana
1 Introduction
2 Cobalt catalysts 2
3 Ruthenium catalysts 4
4 Rhodium catalysts 38
5 Other catalysts 54
6 Reaction mechanism 61
7 Industrial process development 78
8 References 82
Alcohols and Derivatives by Homologation with Syn Gas
G. Braca, A. M Raspolli Galletti and G. Sbrana
1 Introduction 89
2 Hydrocarbonylation of alcohols 90
3 Hydrocarbonylation of aliphatic ethers 123
4 Hydrocarbonylation of carboxylic acid esters 124
5 Homologation of acetic acid in the presence of Ru/iodide or
Rh/iodide catalysts 147
6 Homologation of methyl halides 148
7 Reaction mechanism 148
8 Industrial processes development 179
9 References 181
vi
Hydrocarbonylation of aldehydes and their derivatives
M Marchionna
1 Introduction 191
2 Hydroformylation of formaldehyde to glycol aldehyde 192
3 Hydrocarbonylation of formaldehyde to ethylene glycol 2 I 0
4 Hydrocarbonylation offormaldehyde to acetaldehyde and/or
methanol 213
5 Hydrocarbonylation of formaldehyde to higher oxygenated
products 213
6 Hydrocarbonylation of higher aldehydes 215
7 Conclusions 216
8 References 217
TABLE OF CONTENTS
GLOSSARY OF ABBREVIATIONS
Xlll
PREFACE
xv
G. BRACA, A. M. RASPOLLI GALLETTI and G. SBRANA: Monoalcohols,
Glycols, and their Ethers and Esters by CO Hydrogenation
Department o/Chemistry and Industrial Chemistry, University o/Pisa, ITALY
1 Introduction
2 Cobalt catalysts 2
3 Ruthenium Catalysts 4
3.1 Outline of the research work 4
3.2 Halide promoted ruthenium carbonyl catalysts 6
3.2.1 Ethylene glycol 6
3.3 Iodide promoted ruthenium carbonyl catalysts in phoshine oxide
solvents 8
3.3 .1 Ethanol 8
3.4 Onium salts promoted ruthenium carbonyl catalysts 10
3.4.1 Ethylene glycol and ethanol 10
3.5 Onium halide-Broensted acid promoted ruthenium carbonyl
catalysts 12
3.6 Ruthenium catalytic systems in molten quaternary salts 13
3.6.1 Production of ethylene glycol 15
3.6.2 Production of acetic esters of monoalcohols and glycols 17
3.7 Amine and amine-halide promoted ruthenium carbonyl catalysts 17
3.8 Imidazole promoted ruthenium carbonyl catalysts 20
3.9 Ruthenium-cobalt bimetallic catalytic systems 22
3.9.1 Synthesis of ethanol and/or acetic acid in organic solvents 22
3.9.2 Synthesis of ethanol in molten quaternary onium salts 23
3.9.3 Synthesis of acetic acid in organic solvents 26
3.9.4 Synthesis of acetic acid in molten quaternary onium salts 26
3.9.5 Synthesis of ethylene glycol 29
3.10 Ruthenium-rhodium bimetallic catalytic systems 29
3.10.1 Production of ethylene glycol 29
3.10.2 Production of ethylene glycol acetate 32
3.10.3 Production of ethylene glycol ethers in molten quaternary
salts 32
3.11 Ruthenium-rhenium and ruthenium-manganese bimetallic systems 35
3.12 Conclusive remarks 35
viii
4 Rhodium catalysts 38
4.1 Outline of the research work 38
4.2 Unpromoted rhodium carbonyl catalysts in amides as solvents 40
4.3 Nitrogen base promoted rhodium catalysts 42
4.3.1 Imidazole promoters 42
4.3.2 Alkylamine promoters 43
4.4 Phosphine promoted rhodium catalysts 43
4.4.1 Trialkylphosphines promoters 43
4.4.2 Alkylphosphines-amines promoters 46
4.4.3 Alkylphosphine-protonic acids or phenols promoters 50
4.5 Bimetallic platinum-rhodium catalysts 50
4.6 Conclusive remarks 52
5 Other catalysts 54
5.1 Iridium and rhenium catalysts for ethhylene glycol production 54
5.2 Nickel and copper catalysts for methanol production 57
6 Reaction mechanism 61
6.1 Coordination of CO to a metal centre 62
6.2 Hydrogen activation 62
6.3 Formation of formyl intermediates 68
6.3.1 Cobalt systems 68
6.3.2 Ruthenium systems 68
6.3.3 Rhodium systems 70
6.4 Formation of formaldehyde 70
6.4.1 Ruthenium systems 71
6.4.2 Rhodium systems 72
6.5 Activation of formaldehyde for carbonylation or hydrogenation 72
6.5.1 Cobalt 72
6.5.2 Ruthenium 72
6.5.3 Rhodium 73
6.6 Formation of methanol 73
6.6.1 Cobalt 73
6.6.2 Ruthenium 74
6.6.3 Rhodium 74
6.7 Formation offormic esters 75
6.8 Carbonylation of the hydroxymethyl to hydroxyacetyl intermediate 75
6.9 Hydrogenation of the hydroxyacetyl intermediate to glycolaldehyde 76
6.10 Activation of glycolaldehyde for hydrogenation to ethylene glycol
or carbonylation to glyceryl derivatives 77
6.11 Carbonylation of methanol to acetic acid and homologation to
ethanol 77
6.12 Carbonylation of methanol to methyl formate and hydrogenolysis
of the ester to methanol 77
ix
7 Industrial process development 78
8 References 82
G. BRACA, A.M. RASPOLLI GALLETTI and G. SBRANA: Alcohols and
Derivatives by Homologation with Syn Gas
Department ofC hemistry and Industrial Chemistry, University ofP isa (ITALY)
1 Introduction 89
2 Hydrocarbonylation of alcohols 90
2.1 Methanol hydrocarbonylation 90
2.1.1 Hydrocarbonylation of methanol to ethanol with cobalt
catalysts without iodine 90
2.1.2 Hydrocarbonylation of methanol to acetaldehyde and
1, l-dimethoxyethane with iodide promoted cobalt catalysts 93
2. 1.3 Hydrocarbonylation of methanol with iodine!phosphine!
cobalt systems 95
2.1.4 Hydrocarbonylation of methanol with cobalt-ruthenium
bimetallic systems 102
2.1.5 Hydrocarbonylation of methanol to acetaldehyde with
cobalt-platinum and cobalt-other transition metal catalytic
systems 106
2.1.6 Hydrocarbonylation of methanol to ethanol with ruthenium
catalysts 106
2.1.7 Hydrocarbonylation of methanol to acetaldehyde or ethanol
with rhodium catalysts 109
2.1.8 Hydrocarbonylation of methanol with rhodium-ruthenium
bimetallic systems 110
2.1.9 Methanol homologation with metal carbonyl in the presence
of alkali metal formates 110
2.2 Hydrocarbonylation of higher aliphatic and aromatic alcohols 113
2.2.1 Ethanol 113
2.2.2 Primary aliphatic> C2 alcohols 115
2.2.3 Secondary and tertiary alcohols 118
2.2.4 Benzyl alcohol 118
3 Hydrocarbonylation of aliphatic ethers 123
4 Hydrocarbonylation of carboxylic acid esters 124
4.1 Hydrocarbonylation of methyl acetate 126
4.1.1 Production of ethyl acetate 127
4.1.2 Production of acetaldehyde 131
4.1.3 Production of ethylidenediacetate 131
x
4.1.4 Production of propionic acid 136
4.2 Hydrocarbonylation offormic esters 136
4.3 Hydrocarbonylation of methyl esters of> C2 carboxylic acids 139
4.4. Hydrocarbonylation of esters with > C2 alkoxy groups 141
4.5 Hydrocarbonylation oforthoformic esters 143
5 Homologation of acetic acid in the presence of ruthenium/iodide or
rhodium/iodide catalysts 147
6 Homologation of methyl halides 148
7 Reactiom mechanism 148
7.1 Formation of catalytically active species from precursors 149
7.1.1 Non promoted cobalt systems 156
7.1.2 Iodine promoted cobalt systems 157
7.1.3 Ruthenium systems 158
7.1.4 Non promoted rhodium systems 160
7.1.5 Iodine promoted rhodium systems 160
7.2 Activation oft he substrate and formation of alkyl-metal or
acyl-metal intermediates 161
7.2.1 Non promoted cobalt systems 161
7.2.2 Iodine promoted cobalt systems
7.2.3 Ruthenium systems 164
7.2.4 Rhodium systems 166
7.3 Evolution of the alkyl intermediate 168
7.3.1 Carbonylation of alkyl to acyl intermediates 168
7.3.2 Hydrogenation of the alkyl intermediate to hydrocarbon 170
7.3.3 Isomerization of the alkyl intermediates 171
7.4 Evolution of the acyl intermediate 171
7.4.1 Hydrogenation of acyl intermediates to aldehydes 172
7.4.2 Hydrolysis of acyl intermediates to acids and esters 174
7.4.3 Reductive elimination of acyl iodide 176
7.5 Regeneration of the starting catalytically active species 177
7.6 Activation and hydrogenation of aldehydes to alcohols 177
8 Industrial processes development 179
9 References 181
M. MARCHIONNA: Hydrocarbonylation ofa ldehydes and their derivatives
SNAM PROGETTI S.pA. S.Donato Milanese (ITALY)
1 Introduction 191
2 Hydroformylation of formaldehyde to glycol aldehyde 192
2.1 Cobalt catalysts 193
