Hydroformylation

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Anders Riisager - One of the best experts on this subject based on the ideXlab platform.

  • elucidating the ionic liquid distribution in monolithic silp Hydroformylation catalysts by magnetic resonance imaging
    RSC Advances, 2020
    Co-Authors: Jakob Maximilian Marinkovic, Stefan Benders, Eduardo J Garciasuarez, Alexander Weis, Carsten Gundlach, Marco Haumann, Markus Kuppers, Bernhard Blumich, Rasmus Fehrmann, Anders Riisager
    Abstract:

    Monolithic silicon carbide supported ionic liquid-phase (SILP) Rh-catalysts have very recently been introduced for gas-phase Hydroformylation as an important step toward industrial upscaling. This study investigates the monolithic catalyst system in combination with different impregnation procedures with non-invasive magnetic resonance imaging (MRI). The findings were supported by X-ray microtomography (micro-CT) data of the monolithic pore structure and a catalytic performance test of the catalyst system for 1-butene gas-phase Hydroformylation. MRI confirmed a homogeneous impregnation of the liquid phase throughout the full cross-section of the cylindrical monoliths. Consistent impregnations from one side to the other of the monoliths were achieved with a stabilizer in the system that helped preventing inhomogeneous rim formation. External influences relevant for industrial application, such as long-term storage and temperature exposure, did not affect the homogeneous liquid-phase distribution of the catalyst. The work elucidates important parameters to improve liquid-phase catalyst impregnation to obtain efficient monolithic catalysts for industrial exploitation in gas-phase Hydroformylation as well as other important industrial processes.

  • continuous fixed bed gas phase Hydroformylation using supported ionic liquid phase silp rh catalysts
    Journal of Catalysis, 2003
    Co-Authors: Peter Wasserscheid, Anders Riisager, Roy Van Hal, Rasmus Fehrmann
    Abstract:

    Abstract Continuous flow gas-phase Hydroformylation of propene was performed using novel supported ionic liquid-phase (SILP) catalysts containing immobilized Rh complexes of the biphosphine ligand sulfoxantphos in the ionic liquids 1- n -butyl-3-methylimidazolium hexafluorophosphate and halogen-free 1- n -butyl-3-methylimidazolium n -octylsulfate on silica support. The Rh–sulfoxantphos SILP catalysts proved to be more regioselective than catalysts without ligand and the analogous ionic liquid-free catalysts, giving up to 96% linear product. Furthermore, the performance of the catalysts was generally strongly influenced by the catalyst composition. This is the first report on the use of SILP catalysts for fixed-bed gas-phase Hydroformylation.

  • propene and 1 octene Hydroformylation with silica supported ionic liquid phase silp rh phosphine catalysts in continuous fixed bed mode
    Catalysis Letters, 2003
    Co-Authors: Michael K Eriksen, Anders Riisager, Peter Wasserscheid, Rasmus Fehrmann
    Abstract:

    Supported ionic liquid-phase (SILP) catalysts were made by immobilizing Rh-monophosphine complexes of bis(m-phenylguanidinium)phenylphosphine 1 and NORBOS 2 ligands in 1-n-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF6], on a silica support. The catalysts were active in continuous gas- and liquid-phase Hydroformylation of propene and 1-octene, exhibiting TOFs up to 88 h-1 for SILP Rh-2 catalysts, while only low selectivities up to 74% n-aldehyde (n/iso ratio of 2.8) were obtained. This is the first example of continuous fixed-bed liquid-phase Hydroformylation using SILP catalysts.

Rasmus Fehrmann - One of the best experts on this subject based on the ideXlab platform.

  • elucidating the ionic liquid distribution in monolithic silp Hydroformylation catalysts by magnetic resonance imaging
    RSC Advances, 2020
    Co-Authors: Jakob Maximilian Marinkovic, Stefan Benders, Eduardo J Garciasuarez, Alexander Weis, Carsten Gundlach, Marco Haumann, Markus Kuppers, Bernhard Blumich, Rasmus Fehrmann, Anders Riisager
    Abstract:

    Monolithic silicon carbide supported ionic liquid-phase (SILP) Rh-catalysts have very recently been introduced for gas-phase Hydroformylation as an important step toward industrial upscaling. This study investigates the monolithic catalyst system in combination with different impregnation procedures with non-invasive magnetic resonance imaging (MRI). The findings were supported by X-ray microtomography (micro-CT) data of the monolithic pore structure and a catalytic performance test of the catalyst system for 1-butene gas-phase Hydroformylation. MRI confirmed a homogeneous impregnation of the liquid phase throughout the full cross-section of the cylindrical monoliths. Consistent impregnations from one side to the other of the monoliths were achieved with a stabilizer in the system that helped preventing inhomogeneous rim formation. External influences relevant for industrial application, such as long-term storage and temperature exposure, did not affect the homogeneous liquid-phase distribution of the catalyst. The work elucidates important parameters to improve liquid-phase catalyst impregnation to obtain efficient monolithic catalysts for industrial exploitation in gas-phase Hydroformylation as well as other important industrial processes.

  • continuous fixed bed gas phase Hydroformylation using supported ionic liquid phase silp rh catalysts
    Journal of Catalysis, 2003
    Co-Authors: Peter Wasserscheid, Anders Riisager, Roy Van Hal, Rasmus Fehrmann
    Abstract:

    Abstract Continuous flow gas-phase Hydroformylation of propene was performed using novel supported ionic liquid-phase (SILP) catalysts containing immobilized Rh complexes of the biphosphine ligand sulfoxantphos in the ionic liquids 1- n -butyl-3-methylimidazolium hexafluorophosphate and halogen-free 1- n -butyl-3-methylimidazolium n -octylsulfate on silica support. The Rh–sulfoxantphos SILP catalysts proved to be more regioselective than catalysts without ligand and the analogous ionic liquid-free catalysts, giving up to 96% linear product. Furthermore, the performance of the catalysts was generally strongly influenced by the catalyst composition. This is the first report on the use of SILP catalysts for fixed-bed gas-phase Hydroformylation.

  • propene and 1 octene Hydroformylation with silica supported ionic liquid phase silp rh phosphine catalysts in continuous fixed bed mode
    Catalysis Letters, 2003
    Co-Authors: Michael K Eriksen, Anders Riisager, Peter Wasserscheid, Rasmus Fehrmann
    Abstract:

    Supported ionic liquid-phase (SILP) catalysts were made by immobilizing Rh-monophosphine complexes of bis(m-phenylguanidinium)phenylphosphine 1 and NORBOS 2 ligands in 1-n-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF6], on a silica support. The catalysts were active in continuous gas- and liquid-phase Hydroformylation of propene and 1-octene, exhibiting TOFs up to 88 h-1 for SILP Rh-2 catalysts, while only low selectivities up to 74% n-aldehyde (n/iso ratio of 2.8) were obtained. This is the first example of continuous fixed-bed liquid-phase Hydroformylation using SILP catalysts.

Peter Eilbracht - One of the best experts on this subject based on the ideXlab platform.

  • helicene based phosphite ligands in asymmetric transition metal catalysis exploring rh catalyzed Hydroformylation and ir catalyzed allylic amination
    European Journal of Organic Chemistry, 2011
    Co-Authors: Zuzana Krausova, Peter Eilbracht, Bojan P Bondzic, Petr Sehnal, Serghei Chercheja, I G Stara, David Saman, Ivo Starý
    Abstract:

    Starting from the optically pure [6]helicene-like alcohol(P,3S)-3-methyl-4-(4-methylphenyl)-1,3,6,7-tetrahydrobenzo[c]benzo[5,6]phenanthro[4,3-e]oxepin-14-ol, four helical phosphites were prepared from the corresponding chlorophosphites. These ligands containing parent or substituted 1,3,2-dioxaphospholan-2-yl or dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl moieties were applied to the asymmetric Hydroformylation of terminal alkenes catalyzed by Rh(acac)(CO)2 and the asymmetric allylic amination of cinnamyl-type carbonates catalyzed by [Ir(cod)Cl]2. The helical phosphite containing the dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl group was most successful in the asymmetric Hydroformylation of styrene, leading to moderate enantiomeric excess values (up to 32 % ee), high regioselectivity in favor of the branched product, and mostly high conversion, whereas the helical ligand containing the 4,4,5,5-tetramethyl-1,3,2-dioxaphospholan-2-yl fragment was most effective in asymmetric allylic aminations, exhibiting high enantioselectivity (up to 94 % ee), excellent regioselectivity in favor of the branched products, and good reactivity. This study represents the first use of helicene-like ligands in asymmetric reactions, including Hydroformylation and allylic amination, and the promising results indicate the potential of the helicene moieties as chiral inductors.

  • application of iridium catalyzed allylic substitution reactions in the synthesis of branched tryptamines and homologues via tandem Hydroformylation fischer indole synthesis
    ChemInform, 2009
    Co-Authors: Bojan P Bondzic, Andreas Farwick, Jens X Liebich, Peter Eilbracht
    Abstract:

    Combination of enantioselective allylation reactions with a tandem Hydroformylation–Fischer indole synthesis sequence as a highly diversity-oriented strategy for the synthesis of tryptamines and homologues was explored. This modular approach allows the substituents at C3 of the indole core, the type of the amine moiety, and the distance of the amine moiety to the indole core in the final synthetic step to be defined. The starting materials required for the Hydroformylation step were synthesized viairidium catalyzed enantioselective allylic substitution reactions in high yields and excellent enantioselectivities. The Rh catalyzed Hydroformylation step in the presence of phenyl hydrazine, allows the in situ formed aldehyde to be trapped as the hydrazone. Subsequent acid catalyzed indolization furnishes the desired indole structures in moderate to good yields.

  • 2 3 disubstituted indoles from olefins and hydrazines via tandem Hydroformylation fischer indole synthesis and skeletal rearrangement
    Organic and Biomolecular Chemistry, 2006
    Co-Authors: Petra Linnepe, Axel M Schmidt, Peter Eilbracht
    Abstract:

    The tandem Hydroformylation–Fischer indolisation protocol is used in the synthesis of 2,3-disubstituted indoles. After Hydroformylation of selected olefins to form α-branched aldehydes in a one-pot procedure these are condensed with phenylhydrazine to give hydrazones. Upon acid-promoted [3,3]-sigmatropic rearrangement indolenine intermediates with quaternary centres in the 3-position are formed, which, after selective Wagner–Meerwein-type rearrangement of one of the substituents from the 3- to the 2-position, lead to 2,3-disubstituted indoles. Several olefins, bearing substituents with various functional groups, as well as cyclic olefinic systems are investigated.

Matthew L Clarke - One of the best experts on this subject based on the ideXlab platform.

  • diastereoselective and branched aldehyde selective tandem Hydroformylation hemiaminal formation synthesis of functionalized piperidines and amino alcohols
    Organic Letters, 2017
    Co-Authors: Rachael Pittaway, Jose Fuentes, Matthew L Clarke
    Abstract:

    Starting from readily available allylglycine, a tandem Hydroformylation–hemiaminal formation reaction has been developed for the synthesis of chiral functionalized piperidines, with very good diastereoselectivity and branched regioselectivity using Rh/(S,S,S)-BOBPHOS catalysts. Tandem Hydroformylation–hemiacetal formation also proceeds with good diastereoselectivity (88:12), with the hemiacetal product being hydrogenated with retention of stereochemistry to give a chiral intermediate used in the synthesis of the new antibiotic nemonoxacin.

  • Diastereoselective and Branched-Aldehyde-Selective Tandem Hydroformylation–Hemiaminal Formation: Synthesis of Functionalized Piperidines and Amino Alcohols
    2017
    Co-Authors: Rachael Pittaway, José A. Fuentes, Matthew L Clarke
    Abstract:

    Starting from readily available allylglycine, a tandem Hydroformylation–hemiaminal formation reaction has been developed for the synthesis of chiral functionalized piperidines, with very good diastereoselectivity and branched regioselectivity using Rh/(S,S,S)-BOBPHOS catalysts. Tandem Hydroformylation–hemiacetal formation also proceeds with good diastereoselectivity (88:12), with the hemiacetal product being hydrogenated with retention of stereochemistry to give a chiral intermediate used in the synthesis of the new antibiotic nemonoxacin

  • rapid asymmetric transfer Hydroformylation athf of disubstituted alkenes using paraformaldehyde as a syngas surrogate
    ChemInform, 2015
    Co-Authors: Jose A Fuentes, Rachael Pittaway, Matthew L Clarke
    Abstract:

    As an alternative to conventional asymmetric Hydroformylation (AHF), asymmetric transfer Hydroformylation (ATHF) by using formaldehyde as a surrogate for syngas is reported. A catalyst derived from commercially available [Rh(acac)(CO)2] (acac=acetylacetonate) and 1,2-bis[(2S,5S)-2,5-diphenylphospholano]ethane(1,5-cyclooctadiene) (Ph-BPE) stands out in terms of both activity and enantioselectivity. Remarkably, not only are high selectivities achievable, the reactions are very simple to perform, and higher enantioselectivity (up to 96 % ee) and/or turnover frequencies than those achievable by using the same catalyst (or other leading catalysts) can be obtained by using typical conditions for AHF.

  • phenylphosphatrioxa adamantanes bulky robust electron poor ligands that give very efficient rhodium i Hydroformylation catalysts
    Dalton Transactions, 2005
    Co-Authors: Angharad R Baber, Matthew L Clarke, Katie Heslop, Andrew C Marr, Guy A Orpen, Paul G Pringle, Andrew D Ward, Damaris E Zambranowilliams
    Abstract:

    The cage phosphines 1,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (1a) and 1,3,5,7-tetraethyl-6-phenyl-2,4,8,trioxa-6-phosphaadamantane (1b) have been made by the acid catalysed addition of PhPH2 to the appropriate β-diketones; the acid used (HCl, H3PO4 or H2SO4) and its concentration affect the rate and selectivity of these condensation reactions. Phosphines 1a and 1b react with [PdCl2(NCPh)2] to form complexes trans-[PdCl2(1a)2] (2a) and trans-[PdCl2(1b)2] (2b) as mixtures of rac and meso diastereoisomers. The platinum(II) chemistry is more complicated and when 1a or 1b is added to [PtCl2(cod)], equilibrium mixtures of trans-[PtCl2L2] and [Pt2Cl4L2] (L = 1a or 1b) are formed in CH2Cl2 solution. Meso/rac mixtures of trans-[MCl(CO)(1a)2] M = Ir (6a) or Rh (7a) are formed upon treatment of MCl3·nH2O with an excess of 1a and the anionic cobalt complex [NHEt3][CoCl3(1a)] (9) was isolated from the product formed by CoCl2·6H2O and 1a. The νCO values from the IR spectra of 6a and 7a suggest that 1a resembles a phosphonite in its bonding to Rh and Ir. Crystal structures of meso-2a, meso-2b, rac-6a and 9 are reported and in each case a small intracage C–P–C angle of ca. 94° is observed and this may partly explain the bonding characteristics of ligands 1a and 1b. The cone angles for 1a and 1b are similar and large (ca. 200°). Rhodium complexes of ligands 1a and 1b are Hydroformylation catalysts with similarly high activity to catalysts derived from phosphites. The catalysts derived from 1a and 1b gave unusually low linear selectivity in the Hydroformylation of hexenes. This feature has been further exploited in quaternary-selective Hydroformylations of unsaturated esters; catalysts derived from 1a give better yields and regioselectivities than any previously reported catalyst.

Peter Wasserscheid - One of the best experts on this subject based on the ideXlab platform.

  • rhodium phosphite silp catalysis for the highly selective Hydroformylation of mixed c4 feedstocks
    Angewandte Chemie, 2011
    Co-Authors: Michael Jakuttis, Robert Franke, Marco Haumann, Andreas Schonweiz, Sebastian Werner, Klausdiether Wiese, Peter Wasserscheid
    Abstract:

    The Hydroformylation of alkenes catalyzed by dissolved rhodium complexes is not only one of the largest applications of homogeneous catalysis in industry, but also an established benchmark reaction for testing immobilization concepts for homogeneous catalysts. In recent years, ionic liquids (ILs) as non-aqueous solvents for liquid–liquid biphasic Hydroformylation catalysis have been the subject of intensive study. Important features of ILs compared to the industrial aqueous–organic biphasic catalysis (Ruhrchemie–Rh ne–Poulenc process), are their much better solubility for higher alkenes and their compatibility with phosphite ligands, which readily decompose by hydrolysis in water. Despite these attractive features, we know of no largescale industrial application of ionic liquids in biphasic Hydroformylation catalysis to date. Two important drawbacks of the biphasic ionic liquid systems are the relatively high amounts of expensive IL that are required and its intrinsically high viscosity, which leads to slow mass transport between the two liquid phases. To overcome these limitations, we, among others, have in recent years developed the supported ionic liquid phase (SILP) concept. SILP materials are prepared by dispersing a solution of the catalyst complex in an ionic liquid as a thin, physisorbed film on the large internal surface area of a porous solid material. Since the film thickness of the ionic liquid is within the nanometer range, diffusion problems are minimized by the extremely small diffusion distances. Excellent ionic liquid utilization is achieved; that is, the same catalytic performance can be achieved with a much smaller total IL amount compared to liquid–liquid biphasic systems. Because ionic liquids typically have extremely low vapor pressures, catalysis with SILP materials is particularly attractive in continuous gas-phase contact. During catalysis the immobilized catalytic ionic liquid film comes into contact solely with gaseous reactants and products. For the continuous gas-phase Hydroformylation of pure 1-alkene feedstock, such as, propene and 1-butene, this concept has been demonstrated quite successfully with good catalytic activity (turnover frequencies (TOFs) up to 500 h 1 in the case of propene and 564 h 1 in the case of 1-butene) and excellent catalyst stability (up to 200 h time-on-stream in the case of propene and 120 h in the case of 1-butene) as was demonstrated using a Rh-SILP catalyst modified with the sulfonated phosphine ligand sulfoxantphos (1). The sulfoxantphos–rhodium catalyst is, however, unable to react with internal alkenes such as 2butenes in either Hydroformylation or isomerization. Thus, to convert 1-butene and 2-butenes from a mixed technical C4 feedstock from steam-cracker into the desired linear pentanal, a different catalyst system is required. Rhodium–phosphite complexes are known to be capable of selective isomerization/Hydroformylation activity, which converts internal alkenes in a classical monophase homogeneous catalysis into linear aldehydes with good to excellent selectivity. Most of these ligands, however, are highly airand moisture-sensitive, making it difficult to handle and use them in large quantities and a real challenge to recycle rhodium– phosphite systems. Herein, we show how the new diphosphite ligand 2 in form of a SILP catalyst system is applied in the continuous gas-phase Hydroformylation of an industrial mixed C4 feedstock as illustrated in Scheme 1. Synthesizing 2 and using it in

  • continuous fixed bed gas phase Hydroformylation using supported ionic liquid phase silp rh catalysts
    Journal of Catalysis, 2003
    Co-Authors: Peter Wasserscheid, Anders Riisager, Roy Van Hal, Rasmus Fehrmann
    Abstract:

    Abstract Continuous flow gas-phase Hydroformylation of propene was performed using novel supported ionic liquid-phase (SILP) catalysts containing immobilized Rh complexes of the biphosphine ligand sulfoxantphos in the ionic liquids 1- n -butyl-3-methylimidazolium hexafluorophosphate and halogen-free 1- n -butyl-3-methylimidazolium n -octylsulfate on silica support. The Rh–sulfoxantphos SILP catalysts proved to be more regioselective than catalysts without ligand and the analogous ionic liquid-free catalysts, giving up to 96% linear product. Furthermore, the performance of the catalysts was generally strongly influenced by the catalyst composition. This is the first report on the use of SILP catalysts for fixed-bed gas-phase Hydroformylation.

  • propene and 1 octene Hydroformylation with silica supported ionic liquid phase silp rh phosphine catalysts in continuous fixed bed mode
    Catalysis Letters, 2003
    Co-Authors: Michael K Eriksen, Anders Riisager, Peter Wasserscheid, Rasmus Fehrmann
    Abstract:

    Supported ionic liquid-phase (SILP) catalysts were made by immobilizing Rh-monophosphine complexes of bis(m-phenylguanidinium)phenylphosphine 1 and NORBOS 2 ligands in 1-n-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF6], on a silica support. The catalysts were active in continuous gas- and liquid-phase Hydroformylation of propene and 1-octene, exhibiting TOFs up to 88 h-1 for SILP Rh-2 catalysts, while only low selectivities up to 74% n-aldehyde (n/iso ratio of 2.8) were obtained. This is the first example of continuous fixed-bed liquid-phase Hydroformylation using SILP catalysts.