Hydroformylation E-Book

Armin Börner

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1067

Veröffentlichungsjahr: 2016

Beschreibung

Filling a gap in the market for an up-to-date work on the topic, this unique and timely book in 2 volumes is comprehensive in covering the entire range of fundamental and applied aspects of hydroformylation reactions. The two authors are at the forefront of catalysis research, and unite here their expertise in synthetic and applied catalysis, as well as theoretical and analytical chemistry. They provide a detailed account of the catalytic systems employed, catalyst stability and recovery, mechanistic investigations, substrate scope, and technical implementation. Chapters on multiphase hydroformylation procedures, tandem hydroformylations and other industrially applied reactions using syngas and carbon monoxide are also included. The result is a must-have reference not only for synthetic chemists working in both academic and industrial research, but also for theoreticians and analytical chemists.

Leseprobe

Table of Contents

Cover

Title Page

Copyright

Dedication

Foreword

Volume 1

Introduction

References

Chapter 1: Metals in Hydroformylation

1.1 The Pivotal Role of Hydrido Complexes

References

1.2 Bimetallic Catalysts

References

1.3 Effect of Organic Ligands

References

1.4 Cobalt-Catalyzed Hydroformylation

References

1.5 Rhodium-Catalyzed Hydroformylation

References

1.6 Ruthenium-Catalyzed Hydroformylation

References

1.7 Palladium-Catalyzed Hydroformylation

References

1.8 Platinum-Catalyzed Hydroformylation

References

1.9 Iridium-Catalyzed Hydroformylation

References

1.10 Iron-Catalyzed Hydroformylation

References

Chapter 2: Organic Ligands

References

2.1 Phosphines – Typical Structures and Individuals, Syntheses, and Selected Properties

References

2.2 Phosphites – Synthesis, Typical Examples, and Degradation

References

2.3 Phosphoramidites – Syntheses, Selected Structures, and Degradation

References

2.4 Chiral Phosphorus Ligands for Stereoselective Hydroformylation

References

2.5

N

-Heterocyclic Carbenes (NHCs) as Ligands in Transition-Metal-Catalyzed Hydroformylation

References

Chapter 3: Syngas and Alternative Syngas Sources

3.1 General Remarks

3.2 Generation of Syngas from Formaldehyde or Paraformaldehyde

3.3 Syngas Generation from CO

2

3.4 Syngas Generation from Methanol

3.5 Formic Acid or Methyl Formate as Source for Hydrogen

3.6 Alcohols from Biomass as Source of Syngas

3.7 Conclusions

References

Volume 2

Chapter 4: Hydroformylation Reactions

4.1 Hydroformylation of Unfunctionalized Monoolefins, Polyolefins, and Alkynes

References

4.2 Hydroformylation of Functionalized Olefins

References

4.3 Stereoselective Hydroformylation

References

4.4 Scaffold-Directed Hydroformylation

References

Chapter 5: Tandem and Other Sequential Reactions Using a Hydroformylation Step

References

5.1 Tandem Isomerization–Hydroformylation Reactions

References

5.2 Sequential Hydroformylation–Hydrogenation Reactions

References

5.3 Hydroformylation–Acetalization Tandem Reactions

References

5.4 Hydroaminomethylation

References

5.5 Hydroformylation Followed by Another C−C-Bond Formation Step

References

Chapter 6: Synthesis of Special Products via Hydroformylation

6.1 Production of Aroma Compounds and Fragrances via Hydroformylation

References

6.2 Hydroformylation of Lipids

References

6.3 Hydroformylation of Epoxides

References

6.4 Syngas-Based Routes to Glycol Aldehyde and Ethylene Glycol

References

Chapter 7: Hydroformylation in Nonconventional Reaction Media

7.1 General Remarks

7.2 Methodologies

7.3 Comparison of Some Methods

References

Chapter 8: Decarbonylation and Dehydrocarbonylation of Aldehydes

8.1 General Remarks

8.2 Dehydrocarbonylation

8.3 Conclusions

References

Chapter 9: Selected Aspects of Production Processes

9.1 General Remarks

9.2 The Johnson Matthey Oxo Alcohols Process

TM

9.3 ExxonMobil Process for the Production of Highly Branched, Long-Chain Alcohols

9.4 Process Design for Hydroformylating Octenes at the University of Kansas

9.5 Comments on Heterogenization of Hydroformylation

9.6 Outlook

References

Index

End User License Agreement

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Guide

Cover

Table of Contents

Foreword

Begin Reading

List of Illustrations

Chapter 1: Metals in Hydroformylation

Scheme 1.1 Simplified catalytic cycle for hydroformylation.

Scheme 1.3 Equilibrium of catalytically active hydrido carbonyl complexes.

Scheme 1.2 Competition between isomerization and hydroformylation in relation to CO pressure.

Chapter 2: Organic Ligands

Figure 2.1 Historical development of organic ligands for homogeneously catalyzed hydroformylation.

Figure 2.2 Classification of trivalent P-ligands based on the nature of the α-atom next to the phosphorus.

Figure 2.3 (a, b) Commonly used models for the steric characterization of phosphorus ligands.

Chapter 3: Syngas and Alternative Syngas Sources

Figure 3.1 Sources for syngas used in hydroformylation.

Scheme 3.1 Syngas-free hydroformylation of olefins by a one-pot hydroboration–homologation and final oxidation.

Scheme 3.2 Two competing mechanisms in the hydroformylation with formaldehyde.

Scheme 3.3 Hydroformylation of olefins with paraformaldehyde.

Scheme 3.4 Hydroformylation of allyl alcohol with paraformaldehyde.

Scheme 3.5 Hydroformylation of 1-decene with formalin or paraformaldehyde.

Scheme 3.6 Asymmetric hydroformylation of vinylarenes with formaldehyde (37 wt% aqueous solution).

Scheme 3.7 Tandem hydroformylation–acetalization with formalin and a rhodium catalyst with two different diphosphine ligands.

Scheme 3.8 Hydroformylation of alkynes with formaldehyde as syngas source in aqueous medium.

Scheme 3.9 Synthesis of naturally occurring piperidines by hydroformylation with paraformaldehyde.

Scheme 3.10 Generation of CO by the Ru-catalyzed reversed water gas shift (RWGS) reaction.

Scheme 3.11 Mechanism of the Ru-catalyzed reversed water gas shift (RWGS) reaction.

Figure 3.2 Water gas shift (WGS) reactor system (typical conditions: supported catalyst = 1.4–1.6 g;

p

CO

= 1–12 bar; ; total flow rate = 1.5–195 cm

3

min

−1

;

T

= 100–185 °C).

Scheme 3.12 Ru-catalyzed hydroformylation taking benefit from the reversed water gas shift (RWGS) reaction.

Scheme 3.13 Mechanism of Ru-catalyzed hydroformylation with carbon dioxide (outer circle: production of CO (and H

2

O) and inner circle: hydroformylation followed by hydrogenation).

Scheme 3.14 Tandem hydroformylation–hydrogenation reaction with carbon dioxide.

Figure 3.3 Ethylene hydroformylation with MeOH over a tandem catalyst.

Scheme 3.15 Hydroformylation using formic acid as hydrogen source.

Scheme 3.16 Hydroformylation of isomeric olefins using formic acid as hydrogen source.

Scheme 3.17 Ru-catalyzed conversion of methyl formate into methanol and syngas.

Scheme 3.18 Ru catalyzed hydroformylation of cyclohexene with methyl formate.

Scheme 3.19 One-pot hydroaminomethylation with methyl formate.

Scheme 3.20 Dehydrogenative decarbonylation of 2-naphthylmethanol and formation of gases as a function of time.

Scheme 3.21 Generation of syngas within two separate catalytic reactions via a coordinatively unsaturated iridium complex as connecting link.

Scheme 3.22 Combination of syngas generation from polyols and use in a subsequent hydroformylation.

Volume 2

Figure 4.1 Rate of hydroformylation of an olefin in relation to steric hindrance.

Scheme 4.1 Production of methacrolein via hydroformylation of ethylene.

Scheme 4.2

n

-Regioselective hydroformylation of propylene and important subsequent transformations.

Scheme 4.3 Iso-regioselective hydroformylation of propene.

Scheme 4.4 Sources of isomeric butenes, subsequent

n

-regioselective hydroformylation, and final transformation into 2-propyl-heptanol.

Scheme 4.5 Two-step process for

n

-regioselective hydroformylation of Raffinate II.

Scheme 4.6 Formation of isoprene or 2-alkyl butanoates via iso-selective hydroformylation and subsequent modifications.

Scheme 4.7

n

-Regioselective hydroformylation of various terminal olefins with Rh(BIPHEPHOS).

Scheme 4.8 Manufacture of fuel additives through hydroformylation/acetalization from renewable resources.

Scheme 4.9 Pathways to 1-undecene and 2-methyl-undecanal.

Scheme 4.10 Product distribution in the hydroformylation of 1,3-butadiene.

Scheme 4.11 Hydroformylation of 1,3-butadiene and subsequent transformations.

Scheme 4.12 Hydroformylation of piperylene.

Scheme 4.13 Differences in the hydroformylation of 1,3-butadiene and 1,3-pentadiene.

Scheme 4.14 Hydroformylation of isoprene.

Scheme 4.15 Hydroformylation of cyclopentadiene and dicyclopentadiene.

Scheme 4.16 Hydroformylation of 1,5-hexadiene to pimelaldehyde.

Scheme 4.17 Problems in and alternatives for the hydroformylation of alkynes.

Scheme 4.18 Hydroformylation of alkynes with a self-assembling Rh catalyst.

Scheme 4.19 Hydroformylation of acetylene with a nickel catalyst.

Scheme 4.20 Hydroformylation of alkynes with a homogeneous palladium catalyst.

Chapter 5: Tandem and Other Sequential Reactions Using a Hydroformylation Step

Figure 5.1 Alkylformyl subunit according to the synthon concept.

Chapter 6: Synthesis of Special Products via Hydroformylation

Figure 6.1 Structural correlation between a synthetic and a naturally occurring scent.

Scheme 6.1 Classes of organic compounds relevant to flavoring chemistry accessible via hydroformylation and alternative venues to aldehydes.

Figure 6.2 Different olefinic groups in olfactorius relevant natural compounds.

Figure 6.3 Cyclic mono- and sesquiterpenes bearing a single olefinic group.

Scheme 6.2 Preparation of terminal monoolefins via hydroformylation.

Scheme 6.3 Production of hexyl salicylate via hydroformylation.

Scheme 6.4 Synthesis of mushroom alcohol.

Scheme 6.5 Synthesis of α-hexyl cinnamaldehyde via different hydroformylation protocols.

Scheme 6.6 Hydroformylation of different terminal olefins.

Scheme 6.7 Synthesis of methylnonylacetaldehyde (MNA) and derivatives with interesting olfactorius properties via hydroformylation.

Scheme 6.8 Hydroformylation of α-pinene under different conditions and subsequent transformations.

Scheme 6.9 Production of enantiomerically pure 3-formyl-pinanes via hydroformylation.

Scheme 6.10 Hydroformylation of (−)-β-pinene with different catalytic systems.

Scheme 6.11 Hydroformylation of (−)-β-pinene in the presence of triethylformate or ethanol.

Figure 6.4 Camphene and precursor monoterpenes.

Scheme 6.12 Hydroformylation of camphene.

Figure 6.5 Side products observed in the Pt/Sn-catalyzed hydroformylation of camphene.

Scheme 6.13 Synthesis of Spirambrene® via hydroformylation of 2-carene.

Scheme 6.14 Hydroformylation of isomeric carenes in benzene or ethanol.

Scheme 6.15 Hydroformylation of β-cedrene.

Scheme 6.16 Hydroformylation of cyclooctene.

Scheme 6.17 Synthesis of vertral via hydroformylation.

Scheme 6.18 Synthesis and hydroformylation of bicyclo[3.3.0]-oct-2-ene.

Scheme 6.19 Synthesis of (

E

)-1-cyclopentylethyl but-2-enoate via hydroformylation of cyclopentene.

Scheme 6.20 Hydroformylation of β-citronellene.

Scheme 6.21 Hydroformylation of 5,7-dimethylocta-1,6-diene.

Scheme 6.22 Hydroformylation of 2,6-dimethylhepta-1,5-diene and 2,6-dimethylocta-1,5-diene.

Scheme 6.23 Hydroformylation of 3-methylocta-2,6-diene.

Scheme 6.24 Hydroformylation of polyolefins and subsequent hydrogenation.

Scheme 6.25 Pathways to 10-undecen-1-ol.

Scheme 6.26 Hydroformylation of 1,5-cyclooctadiene.

Scheme 6.27 Hydroformylation of 2,6-dimethyl-1,5-cyclooctadiene.

Scheme 6.28 Hydroformylation of dicyclopentadiene.

Figure 6.6 Limonene and some related compounds.

Scheme 6.29 Hydroformylation of (

R

)-(+)-limonene under different reaction conditions.

2

Scheme 6.30 Hydroformylation of (

R,R

)-

trans

-isolimonene in the presence of triethyl orthoformate.

Scheme 6.31 Synthesis of terpinolene aldehyde from different precursors and under different hydroformylation conditions.

Scheme 6.32 Hydroformylation of γ-terpinene.

Scheme 6.33 Hydroformylation of bicyclo[4.3.0]nona-3,7-diene.

Scheme 6.34 Hydroformylation of (−)-β-caryophyllene.

Scheme 6.35 Hydroformylation of caryophyllene oxide.

Scheme 6.36 Hydroformylation of isoprene.

Scheme 6.37 Hydroformylation of myrcene with different Rh catalysts.

Scheme 6.38 Hydroformylation of (

E

,

E

)-α-farnesene.

Scheme 6.39 Hydroformylation of α-terpinene.

Scheme 6.40 Hydroformylation of 2-methyldodec-11-en-2-ol.

Scheme 6.41 Preparation of hydroxycitronellal and related hydroxy aldehydes.

Scheme 6.42 Hydroformylation of 3,7-dimethylocten-1-en-7-ol.

Scheme 6.43 Hydroformylation of long-chain hydroxy diolefins and subsequent hydrogenation.

Scheme 6.44 Synthesis of plinol from linalool and subsequent transformations.

Scheme 6.45 Synthesis and hydroformylation of α-terpineol.

Scheme 6.46 Hydroformylation of (

S

)-(−)-perillyl alcohol.

Scheme 6.47 Hydroformylation of norbornenyl isopropanol.

Scheme 6.48 Hydroformylation/acetalization of linalool under different reaction conditions.

Scheme 6.49 Hydroformylation–hemiacetalization of (−)-myrthenol.

Scheme 6.50 Hydroformylation–hemiacetalization of isopulegol.

Scheme 6.51 Hydroformylation–acetalization–dehydration of (+)-8(15)-cedren-9-ol.

Scheme 6.52 Hydroformylation–acetalization of nerolidol.

Scheme 6.53 Synthesis of guaiazulene via hydroformylation.

Scheme 6.54 Hydroformylation of β-isophorone and subsequent reactions.

Scheme 6.55 Hydroformylation of carvone.

Scheme 6.56 Hydroformylation of dihydrocarvone.

Scheme 6.57

n

-Regioselective hydroformylation of styrene and subsequent hydrogenation.

Scheme 6.58 Hydroformylation of indene and subsequent hydrogenation.

Figure 6.7 Indanyl-2-carbaldehydes with structural similarities to Bourgeonal®.

Scheme 6.59 Synthesis of Florhydral® via hydroformylation.

Scheme 6.60 Hydroformylation of α-substituted styrenes.

Scheme 6.61 Hydroformylation of

p

-(isopropenyl)phenyl dimethylcarbinol.

Figure 6.8 Naturally occurring propenylarenes.

Scheme 6.62 Double bond isomers of propenylarenes.

Scheme 6.63 Preparation of anethole.

Figure 6.9 Prominent scents based on 3-aryl-2-methylpropanals.

Scheme 6.64 Hydroformylation of eugenol with different phosphine ligands.

Scheme 6.65 Hydroformylation of 1-aryl-prop-1-enes.

Scheme 6.66 Hydroformylation of different 1-aryl-prop-1-enes in methanol (for R

1

–R

3

compare Table 6.3).

Scheme 6.67 Preparation and hydroformylation of 1-aryl-enolethers.

Scheme 6.68 Asymmetric hydroformylation of 1-phenyl-prop-1-ene.

Scheme 6.69 Asymmetric hydroformylation of aryl propenes.

Scheme 6.70 Hydroformylation of α-branched aryl olefins.

Scheme 6.71 Substrates and hydroformylation of various olefins.

Scheme 6.72 Hydroformylation of vinyl-aryl ethers.

Scheme 6.73 Preparation of 4,7-dihydro-1,3-dioxepines and subsequent hydroformylation.

Scheme 6.74 Hydroformylation of the orange flower ether.

Scheme 6.75 Reductive hydroformylation of (+)-limonene.

Scheme 6.76 Hydroformylation–cyclization of (+)-limonene.

Scheme 6.77 Hydroformylation–(aldol condensation)–hydrogenation tandem reaction and possible chemical targets.

Scheme 6.78 Pd-catalyzed hydroformylation of alkynes and potential chemical targets.

Scheme 6.79 Challenges for hydroformylation in the future.

Chapter 7: Hydroformylation in Nonconventional Reaction Media

Figure 7.1 Phosphorus ligands linked to polymeric supports.

Scheme 7.1 Synthesis of a polymeric soluble hydroformylation catalyst by anion exchange.

Figure 7.2 Frequently used sulfonated phosphine ligands.

Figure 7.3 Solubility of olefins and their corresponding aldehydes in water.

Figure 7.4 Phosphine ligands with pH-dependent solubility properties.

Figure 7.5 Randomly methylated cyclodextrines used together with a trisulfonated diphenylphosphine ligand for the improvement of mass transfer.

Figure 7.6 Rate of the hydroformylation (indicated by decrease of syngas pressure) in the hydroformylation of 1-olefins with a rhodium TPPTS catalyst effected by adding [OMIM]Br (0.5 mol dm

−3

).

Scheme 7.2 Switchable catalyst system based on the ligand Tris-SwitchPhos.

Scheme 7.3 Degradation of a triarylphosphine in an aqueous medium.

Figure 7.7 Ligand concentration versus operating time in the Ruhrchemie/Rhône-Poulenc process.

Scheme 7.4 Reaction of an acidic hydroformylation catalyst with water.

Scheme 7.9 Aqueous two-phase hydroformylation with a water-soluble rhodium catalyst and an additional promoter ligand.

Scheme 7.5 Comparison of the rhodium-catalyzed hydroformylation of methyl acrylate in an organic and in an aqueous two-phase system.

Scheme 7.6 Hydroformylation of acrylates under SAPC conditions.

Scheme 7.7 Hydroformylation of 1-decene in water in the presence of methylated cyclodextrines.

Scheme 7.8 Hydroformylation of technical-grade methyl oleate in water in the presence of activated carbon.

Figure 7.8 Fluorinated solvents.

Figure 7.9 Miscibility diagrams of 1-decene/1

H

-perfluorooctane and

n

-undecanal/1

H

-perfluorooctane.

Figure 7.10 Trivalent phosphorus ligands used in rhodium-catalyzed hydroformylation in fluorous biphasic hydroformylation.

Scheme 7.10 Decomposition of fluorinated triaryl phosphites in the presence of aldehydes.

Figure 7.11 Schematic phase diagram of CO

2

with snapshots from the liquid/gas region to the supercritical region (a CO

2

-soluble rhodium complex is responsible for the bright orange color).

Scheme 7.11 Cobalt-catalyzed hydroformylation of propene in scCO

2

.

Scheme 7.12 Rhodium-catalyzed hydroformylation of

trans

-2-hexene in toluene or scCO

2

.

Scheme 7.13 Rh(PEt

3

)-catalyzed hydroformylation of 1-hexene in toluene or scCO

2

.

Figure 7.12 Phosphorus or fluorinated acetylacetone ligands and anions for cationic rhodium complexes specially designed for rhodium-catalyzed hydroformylation in supercritical carbon dioxide bearing fluoro-substituents.

Scheme 7.14 Asymmetric hydroformylation of styrene in scCO

2

with a specially designed (

R,S

)-BINAPHOS ligand.

Figure 7.13 Selective hydroformylation of 1-octene out of a mixture of 1-octene/1-octadecene (1 : 1) by taking benefit from different solubilities at different CO

2

pressures (HRh(CO)(TPPTS)

3

, CO/H

2

(20 bar), 80 °C, 20 h).

Scheme 7.15 First hydroformylation attempt in ionic liquids.

Figure 7.17 Typical cations and salts of ionic liquids and the order of 1-hexene solubility in [BMIM][X] in dependence on the anion X.

Figure 7.14 Halogen-free ionic liquids derived from sulfonates.

Figure 7.15 Turnover frequency of 1-hexene solubility in the ionic liquids. Reaction conditions: Rh(acac)(CO)

2

(0.075 mmol), 1-hexene/Rh = 800, TPPMS/Rh = 4, CO/H

2

= 2 MPa, 80 °C; TOF determined at 25% conversion of 1-hexene.

Figure 7.16 Ligands specially designed for the two-phase reaction in ionic liquids.

Scheme 7.16 Cobalt-containing ionic liquids and an activation mode for the precatalyst anion.

Scheme 7.17 Reaction of a phosphite ligand with a fluorinated anion.

Figure 7.18 Supported ionic liquid catalysis applied in the hydroformylation of 1-hexene (tppti = tri(

m

-sulfonyl)triphenyl phosphine tris(1-butyl-3-methyl-imidazolium) salt.

Figure 7.19 Schematic of the reactor system used for the continuous flow SILP reaction.

Figure 7.20 Possible interactions of Sulfoxantphos (

A

and

B

) and [BMIM][OctSO

4

] ionic liquid (

C

) on silica support [113].

Figure 21 Principle of temperature-dependent multicomponent solvent systems.

Scheme 7.18 Hydroformylation in a TMS system.

Chapter 8: Decarbonylation and Dehydrocarbonylation of Aldehydes

Scheme 8.1 Decarbonylation and dehydrocarbonylation.

Scheme 8.2 Rhodium-catalyzed decarbonylation of an α,β-unsaturated aldehyde.

Scheme 8.3 Rhodium-catalyzed decarbonylation of

n

-heptanal.

Scheme 8.4 Rhodium-catalyzed decarbonylation of heptanal with rhodium complexes bearing chelating diphosphine ligands.

Scheme 8.5 Synthesis of a rhodium triphos catalyst and the mechanism of the catalytic decarbonylation of aldehydes.

Scheme 8.6 Side products in the rhodium-catalyzed decarbonylation of pent-4-enal in the presence of ethylene.

Scheme 8.7 Decarbonylation of 1-nonanol by a tandem (Oppenhauer oxidation)–decarbonylation sequence.

Scheme 8.8 Rhodium-catalyzed decarbonylation of 3-methyl-3-phenylbutanal.

Scheme 8.9 Rhodium-catalyzed removal of a formyl group in the total synthesis of a steroid.

Scheme 8.10 Removal of a formyl group in the total synthesis of a neurosteroid analog.

Scheme 8.11 Rhodium(triphos)-catalyzed decarbonylation of aldehydes.

Scheme 8.12 Iridium-catalyzed decarbonylation of aldehydes.

Scheme 8.13 Rhodium-catalyzed decarbonylation of an aldehyde derived from a Diels–Alder reaction.

Figure 8.1 Gas–liquid continuous-flow decarbonylation of aldehydes with N

2

as stripping gas. (P = HPLC pump, SL = sample loop, M = mixer, RT = residence tube, HE = heat exchanger, and BPR = backpressure regulator).

Scheme 8.14 Rhodium-catalyzed dehydrocarbonylation–hydroformylation reaction.

Scheme 8.15 Cobalt-catalyzed decarbonylation of aryl substituted 1-propanols.

Scheme 8.16 Dehydroformylation of aldehydes.

Scheme 8.17 Mechanism of the dehydroformylation.

Scheme 8.18 Synthesis of (+)-yohimbenone and other products via dehydroformylation (arrows indicated the place of reaction).

Chapter 9: Selected Aspects of Production Processes

Figure 9.1 Principle of the JM process based on [4].

Figure 9.2 Simplified block flow diagram of the process. Explanations: (1.1)–(1.5): hydroformylation reactor; (2): cooler and liquid/gas separator; (3) gas recycling; (4) syngas compression; (5) cooling exchanger; (6) separators; (7) hydrogenation; (8) separator; and (9) downstreaming.

Scheme 9.1 Side reactions that consume reaction gas.

Scheme 9.2 Basic reactions of decobalting in the ExxonMobil process.

Figure 9.3 Setup for the CXL process according to [16].

Figure 9.4 Annual costs for different processes according to Ref. [16].

Scheme 9.3 Synthesis of POL-TPP.

Figure 9.5 Setup for a process for the hydroformylation of short-chain and long-chain olefins using heterogeneous catalyst systems based on porous organic ligands according to [20]b. Pressure controller (PC), flow indicator (FI), and pressure indicator (PI).

List of Tables

Chapter 3: Syngas and Alternative Syngas Sources

Table 3.1 Rh catalyzed hydroformylation of 1-octene with formaldehyde/H

2

a

Volume 2

Table 4.1 Large-scale hydroformylation processes of propylene under different conditions

Chapter 6: Synthesis of Special Products via Hydroformylation

Table 6.1 Hydroformylation of linear aliphatic monoolefins with Rh(BIPHEPHOS)

Table 6.2 Position of the CHO group after the hydroformylation of eugenol and isoeugenol as a function of temperature

Table 6.3 Hydroformylation of different 1-aryl-prop-1-enes

Table 6.4 Hydroformylation of allyl ethers and perfumery properties

Table 6.5 Hydroformylation of branched allyl ethers and perfumery properties

Chapter 7: Hydroformylation in Nonconventional Reaction Media

Table 7.1 Comparison of hydroformylation reaction of 1-hexene or 1-octene in different nonconventional reaction media

Chapter 9: Selected Aspects of Production Processes

Table 9.1 Specific investment in million $ according to [16]

Table 9.2 Data for the hydroformylation of 1-octene according to [21]

Armin Börner and Robert Franke

Hydroformylation

Fundamentals, Processes, and Applications in Organic Synthesis

Volume 1

Armin Börner and Robert Franke

Hydroformylation

Fundamentals, Processes, and Applications in Organic Synthesis

Volume 2

Authors

Armin Börner

Institut für Chemie

Universitä t Rostock

Albert-Einstein-Str. 3a

18059 Rostock

Germany

and

Leibniz-Institut für Katalyse

an der Universitä t Rostock e.V.

Albert-Einstein-Str. 29a

18059 Rostock

Germany

Robert Franke

Evonik Performance Materials GmbH

Paul-Baumann-Straße 1

45772 Marl

Germany

and

Lehrstuhl für Theoretische Chemie

Ruhr-Universitä t Bochum

44780 Bochum

Germany

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