US20050209455A1 - Bisphosphines as bidentate ligands - Google Patents

Bisphosphines as bidentate ligands Download PDF

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US20050209455A1
US20050209455A1 US10/508,537 US50853705A US2005209455A1 US 20050209455 A1 US20050209455 A1 US 20050209455A1 US 50853705 A US50853705 A US 50853705A US 2005209455 A1 US2005209455 A1 US 2005209455A1
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alkyl
cycloalkyl
aryl
ligand
group
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Armin Boerner
Jens Holz
Axel Monsees
Thomas Riermeier
Renat Kadyrov
Carsten Schneider
Uwe Dingerdissen
Karlheinz Drauz
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Evonik Operations GmbH
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Degussa GmbH
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Assigned to DEGUSSA AG reassignment DEGUSSA AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DINGERDISSEN, UWE, KADYROV, RENAT, MONSEES, AXEL, HOLZ, JENS, RIERMEIER, THOMAS, BOERNER, ARMIN, DRAUZ, KARLHEINZ, SCHNEIDER, CARSTEN A.
Publication of US20050209455A1 publication Critical patent/US20050209455A1/en
Priority to US11/609,606 priority Critical patent/US7361786B2/en
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    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
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    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
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    • B01J31/2433—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2461—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring
    • B01J31/2471—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring with more than one complexing phosphine-P atom
    • B01J31/2476—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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Definitions

  • the present invention relates to bisphosphines as bidentate ligands, a process for the production thereof and their use.
  • the invention concerns bisphosphines of the general structure (I).
  • Enantiomer-enriched chiral ligands are used in asymmetric synthesis or asymmetric catalysis. It is essential here for the electronic and stereochemical properties of the ligand to be optimally adapted to the particular catalysis problem. An important aspect of the success of these families of compounds is attributed to the creation of a particularly asymmetric environment of the metal centre by these ligand systems. To utilise such an environment for an effective transfer of chirality, it is advantageous to control the flexibility of the ligand system as an inherent limitation of the asymmetric induction.
  • cyclic phosphines particularly the phospholanes
  • chiral phospholanes are, for example, the DuPhos and BPE ligands used in asymmetric catalysis. Ideally, therefore, a chiral ligand basic skeleton capable of versatile modification is available, which can be varied within broad limits in respect of its steric and electronic properties.
  • the object of this invention is therefore to provide a ligand skeleton analogous to that of the existing phospholane ligands, but which can additionally be varied and used within broad limits and possesses comparably good catalytic properties.
  • the invention is based on the object of providing novel, asymmetric, bidentate and chiral phosphine ligand systems for catalytic purposes, which can be produced simply and with high enantiomeric purity.
  • the ligands according to the invention preferably correspond to structures of the general formula (II), wherein
  • the ligand systems according to the invention can therefore be attached to a polymer enlargement.
  • the ligands or the complexes/catalysts that can be produced from them can thus be separated very readily from the low molecular-weight compounds, e.g. by filtration, owing to the link to the polymer enlargement, and are thus accessible to the recycling desired by the invention, which is extremely simple but nonetheless advantageous.
  • the ligands/complexes can be enlarged in molecular weight by linking to a polymer enlargement, and optionally heterogenised in this way.
  • the enantioselective hydrogenation with complexes or catalysts that have been thus enlarged in molecular weight can therefore proceed in both a homogeneous and a heterogeneous phase.
  • the polymer enlargement can be freely selected within the framework of the invention. It is limited on the one hand by considerations of practicability and costs, and on the other hand by prevailing technical conditions (retention capacity, solubility etc.).
  • Some polymer enlargements for catalysts are known from the prior art (Reetz et al., Angew. Chem. 1997, 109, 1559f.; Seebach et al., Helv. Chim Acta 1996, 79, 1710f.; Kragl et al., Angew. Chem. 1996, 108, 684f.; Schurig et al., Chem. Ber./Recueil 1997, 130, 879f.; Bolm et al., Angew. Chem.
  • polymer enlargement it is also preferred for the polymer enlargement to be formed by polyacrylates, polyacrylamides, polyvinylpyrrolidinones, polysiloxanes, polybutadienes, polyisoprenes, polyalkanes, polystyrenes, polyoxazolines or polyethers, or mixtures thereof.
  • polystyrenes are used to construct the polymer enlargement.
  • linker serves to create a distance between ligand and polymer to reduce or eliminate mutual interactions that are disadvantageous to the reaction.
  • linkers can, in principle, be freely selected by the person skilled in the art. They should be selected according to the aspects of how well they can be coupled to the polymer/monomer on the one hand and to the ligand on the other hand. Suitable linkers can be found e.g. in the literature references mentioned above under the heading of “Polymer enlargement”.
  • linkers such as e.g. 1,4′-biphenyl, 1,2-ethylene, 1,3-propylene, PEG-(2-10), ⁇ , ⁇ -siloxanylene or 1,4-phenylene as well as ⁇ , ⁇ -1,4-bisethylenebenzene or linkers obtainable from siloxanes of the general formula IV are especially preferred.
  • the size of the polymer enlargement should preferably be calculated such that the actual catalyst (formed from optionally polymer-enlarged ligand and transition metal) dissolves in the solvent to be used, so work can be performed in a homogeneous phase.
  • the polymer-enlarged complex/catalyst used is preferably therefore a homogeneously soluble one. As a result, negative effects, which occur as a result of the phase change of the substrates and products otherwise necessary with the use of heterogeneous catalysts, can be avoided.
  • the polymer-enlarged ligands can have an average molecular weight in the range of 1,000-1,000,000, preferably 5,000-500,000, particularly preferably 5,000-300,000, g/mol.
  • linkers/ligands can be attached to the polymer enlargement:
  • Polymers according to a) or b) can optionally be prepared and block-copolymerised with other polymers, which also exhibit the active units causing the chiral induction (ligand) or which do not exhibit them.
  • the number of linkers/ligands per monomer in the polymer that as many as possible of these catalytically active units (ligands) should be accommodated in a polymer, so that the conversion per polymer enlargement is increased as a result.
  • the ligands should be sufficiently spaced apart so that a reciprocal negative effect on the reactivity (TOF, selectivity) is minimised or completely avoided.
  • the distance between the linkers/ligands in the polymer should be in the range of 1-200 monomer units, preferably 5-25 monomer units.
  • those positions in the polymer or monomer to be polymerised that can readily be functionalised, or allow an existing functionality to be used for the link are used for attaching the linker/ligand.
  • heteroatoms or unsaturated carbon atoms are preferably suitable for constructing the link.
  • the existing aromatics can be used as connecting points to the linkers/ligands.
  • Functionalities can be readily attached to these aromatics, preferably in 3-, 4- or 5-position, particularly preferably in 4-position, by means of standard aromatic chemistry.
  • Advantageously suitable for this purpose are e.g. para-hydroxy-, para-chloromethyl- or para-aminostyrene derivatives.
  • an acid group or ester group is present in the monomer component in each case, to which the linker or the active unit can be linked before or after the polymerisation, preferably via an ester or amide bond.
  • Polysiloxanes as polymer enlargement are preferably constructed in such a way that, in addition to dimethylsilane units, hydromethylsilane units are also present.
  • the linkers/ligands can then also be attached to these positions by a hydrosilylation.
  • These can preferably be linked to the functionalities under consideration in the polymer under hydrosilylation conditions (overview of the hydrosilylation reaction by Ojima in The Chemistry of Organic Silicon Compounds, 1989 John Wiley & Sons Ltd., 1480-1526).
  • Suitable polysiloxanes modified in this way are known in the literature (“Siloxane polymers and copolymers” White et al., in Ed. S. Patai “The Chemistry of Organic Silicon Compounds” Wiley, Chichester, 1989, 46, 2954; C. Wandrey et al. TH: Asymmetry 1997, 8, 1975).
  • linker attachment to the active units can preferably take place via heteroatoms or certain functionalities such as C ⁇ O, CH 2 , O, N, S, P, Si or B, ether-/thioether bonds, amine bonds or amide bonds preferably being linked, or esterifications, alkylations, silylations and additions to double bonds being carried out.
  • certain functionalities such as C ⁇ O, CH 2 , O, N, S, P, Si or B, ether-/thioether bonds, amine bonds or amide bonds preferably being linked, or esterifications, alkylations, silylations and additions to double bonds being carried out.
  • the ligands according to the invention shown should, if possible, possess a high enantiomeric purity.
  • the compounds of formulae (I) to (IV) should preferably possess an enantiomeric enrichment of >90%, more preferably >98%.
  • Another aspect of the invention provided relates to complexes containing the ligands according to the invention with at least one transition metal.
  • Palladium, platinum, rhodium, ruthenium, osmium, iridium, cobalt, nickel or copper, in any catalytically relevant oxidation stage, are suitable as transition metals.
  • These complex compounds are obtainable in solution by simply adding the ligands according to the invention to metal complex precursors, with which the person skilled in the art is familiar.
  • the invention also relates to a process for the production of the ligands according to the invention, wherein the corresponding phosphines are obtained by reacting LiP(SiMe 3 ) 2 with corresponding co-reactants provided with nucleofuge leaving groups in the presence of an organometallic base.
  • Alkyl metals such as e.g. n-, sec-, tert.-BuLi, MeLi, or the like, can be used as the organometallic base.
  • the trimethylsilylphosphines thus obtained are preferably reacted with the corresponding dihalogen derivative of the structures of group A illustrated above, the halogen atoms each being positioned on the free valencies of the structures shown.
  • the procedure is to react an enantiomer-enriched sulfate with a phosphine in the presence of a strong base to form the monophospholane.
  • the phosphorus-carbon bond is split with the aid of an alkali metal and converted to silyl phospholane by adding a halogen silyl compound.
  • the silyl phospholane is reacted with 2,3-dichloromaleic anhydride or a 2,3-dichloromaleamide derivative to form the bisphospholane.
  • the diol is converted to the dimesylate in the presence of a nitrogen base and then converted to the phospholane in the presence of Li 2 PPh 2 -THF ( Tetrahedron Asymmetry 1991, 2, 569-592).
  • the phospholane is also obtained by reacting the cyclic sulfate with H 2 PPh in the presence of an alkali metal hydride ( J. Am. Chem. Soc. 1999, 121, 9899-9900).
  • Another alternative preparation of the phospholane is achieved by reacting the cyclic sulfate with phenylphosphine in the presence of butyllithium.
  • the P-silylated compound is obtained by adding trimethylsilyl chloride.
  • the compounds of the general formulae (I)-(IV) can be used as ligands for complex compounds in asymmetric, metal-catalysed reactions (such as e.g. hydrogenation, hydroformylation, rearrangement, allylic alkylation, cyclopropanation, hydrosilylation, hydride transfers, hydroborations, hydrocyanations, hydrocarboxylations, aldol reactions or Heck reaction). They are particularly suitable for asymmetric reactions.
  • Suitable complexes contain ligands according to the invention of formulae (I)-(IV) as ligands, [M x P y L z S q ]A r (V) wherein, in general formula (V), M denotes a metal centre, preferably a transition metal centre, L denotes the same or different, coordinating, organic or inorganic ligands and P denotes bidentate organophosphorus ligands of formulae (I)-(IV) according to the invention, S represents coordinating solvent molecules and A represents equivalents of non-coordinating anions, wherein x and y are whole numbers greater than or equal to 1, and z, q and r are whole numbers greater than or equal to 0.
  • the sum of y+z+q has an upper limit set by the coordination centres available at the metal centres, it being unnecessary for all the coordination positions to be occupied.
  • Complex compounds with an octahedral, pseudo-octahedral, tetrahedral, pseudo-tetrahedral or square-planar coordination sphere, which can also be distorted around the transition metal centre in each case, are preferred.
  • the sum of y+z+q is less than or equal to 6 in these complex compounds.
  • the complex compounds according to the invention contain at least one metal atom or ion, preferably a transition metal atom or ion, particularly of palladium, platinum, rhodium, ruthenium, osmium, iridium, cobalt, nickel or copper in any catalytically relevant oxidation stage.
  • a transition metal atom or ion particularly of palladium, platinum, rhodium, ruthenium, osmium, iridium, cobalt, nickel or copper in any catalytically relevant oxidation stage.
  • Complex compounds with fewer than four metal centres are preferred, and those with one or two metal centres are particularly preferred.
  • the metal centres can be occupied by various metal atoms and/or ions.
  • Preferred ligands L of these complex compounds are halide, particularly Cl, Br and I, diene, particularly cyclooctadiene, norbornadiene, olefin, particularly ethylene and cyclooctene, acetato, trifluoroacetato, acetylacetonato, allyl, methallyl, alkyl, particularly methyl and ethyl, nitrile, particularly acetonitrile and benzonitrile, and also carbonyl and hydrido ligands.
  • Preferred coordinating solvents S are amines, particularly triethylamine, alcohols, particularly methanol and aromatics, particularly benzene and cumene.
  • Preferred non-coordinating anions A are trifluoroacetate, trifluoromethane sulfonate, BF 4 , ClO 4 , PF 6 , SbF 6 and BAr 4 .
  • metal-ligand complex compounds can take place in situ by the reaction of a metal salt or a corresponding pre-complex with the ligands of the general formulae (I)-(IV).
  • a metal-ligand complex compound can be obtained by reaction of a metal salt or a corresponding pre-complex with the ligands of the general formulae (I)-(IV) and subsequent isolation.
  • metal salts are metal chlorides, bromides, iodides, cyanides, nitrates, acetates, acetylacetonates, hexafluoroacetylacetonates, tetrafluoroborates, perfluoroacetates or triflates, particularly of palladium, platinum, rhodium, ruthenium, osmium, iridium, cobalt, nickel or copper.
  • the complex compounds based on one or more metals of the metallic elements can already be catalysts or can be used to produce catalysts based on one or more metals of the metallic elements, particularly from the group of Ru, Co, Rh, Ir, Ni, Pd, Pt and Cu. All these complex compounds are particularly suitable in the asymmetric hydrogenation of C ⁇ C—, C ⁇ O— or C ⁇ N-bonds, in which they exhibit high activities and selectivities, and in asymmetric hydroformylation.
  • the ligands of the general formulae (I)-(IV) can be very well adapted, sterically and electronically, to the particular substrate and the catalytic reaction owing to their simple, broad adaptability.
  • Corresponding catalysts contain at least one of the complex compounds according to the invention.
  • the use of the complexes or catalysts according to the invention is particularly suitable for the hydrogenation of E/Z mixtures of prochiral N-acylated ⁇ -aminoacrylic acids or their derivatives.
  • Acetyl, formyl or urethane or carbamoyl protective groups can preferably be used here as the acyl group.
  • the ligands and complexes/catalysts are used in a way known to the person skilled in the art in the form of transfer hydrogenation (“Asymmetric transfer hydrogenation of C ⁇ O and C ⁇ N bonds”, M. Wills et al. Tetrahedron: Asymmetry 1999, 10, 2045; “Asymmetric transfer hydrogenation catalyzed by chiral ruthenium complexes” R. Noyori et al. Acc. Chem. Res. 1997, 30, 97; “Asymmetric catalysis in organic synthesis”, R. Noyori, John Wiley & Sons, New York, 1994, p. 123; “Transition metals for organic Synthesis” Ed. M. Beller, C.
  • the preferred procedure is to dissolve the substrate to be hydrogenated and the complex/catalyst in a solvent.
  • the catalyst is preferably formed from a pre-catalyst as indicated above, in the presence of the chiral ligand, by reaction or by pre-hydrogenation before the substrate is added. Hydrogenation is then performed at 0.1 to 10 bar, preferably 0.5 to 5 bar, hydrogen pressure.
  • the temperature during hydrogenation should be selected such that the reaction proceeds sufficiently rapidly with the desired enantiomeric excesses, but side reactions are avoided as far as possible. It is advantageous to work at temperatures of ⁇ 20° C. to 100° C., preferably 0° C. to 50° C.
  • the ratio of substrate to catalyst is determined by economic factors.
  • the reaction should be carried out sufficiently rapidly with the lowest possible complex/catalyst concentration. However, it is preferable to work with a substrate/catalyst ratio of between 10000:1 and 10:1, preferably 1000:1 and 50:1.
  • the use of the polymer-enlarged ligands or complexes is advantageous in catalytic processes carried out in a membrane reactor.
  • the continuous operation that is possible in this apparatus, in addition to batch and semi-continuous operation, can be carried out in the cross-flow filtration mode ( FIG. 2 ) or as dead-end filtration ( FIG. 1 ), as desired.
  • a complex/catalyst For a complex/catalyst to appear suitable for use in a membrane reactor, it has to fulfil many different criteria. On the one hand, for example, it should be ensured that there must be a sufficiently high retention capacity for the polymer-enlarged complex/catalyst so that there is satisfactory activity in the reactor over a desired period, without complex/catalyst having to be continually added, which is disadvantageous from the point of view of process economy (DE19910691).
  • the catalyst used must have an appropriate tof (turn over frequency), to be able to convert the substrate into the product within economically reasonable periods.
  • mixtures of polymer-enlarged polymers refer to the fact that individual polymers of different origins are polymerised together into block polymers. Random mixtures of the monomers in the polymer are also possible.
  • Polymer enlargement within the framework of the invention refers to the fact that one or more active units causing chiral induction (ligands) are copolymerised in a suitable form with other monomers or that these ligands are attached to an existing polymer by methods known to the person skilled in the art.
  • ligands active units causing chiral induction
  • Forms of the units suitable for copolymerisation are well known to the person skilled in the art and can be freely selected by him.
  • the procedure is preferably such that the molecule in question is derivatised with groups capable of copolymerisation, according to the type of copolymerisation, e.g. in the case of copolymerisation with (meth)acrylates, by attaching to acrylate molecules.
  • Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl or octyl, together with all their bond isomers, can be considered as (C 1 -C 8 )-alkyl radicals.
  • the (C 1 -C 8 )-alkoxy radical corresponds to the (C 1 -C 8 )-alkyl radical, with the proviso that this is bonded to the molecule via an oxygen atom.
  • radicals in which the alkyl chain is interrupted by at least one oxygen function are meant, wherein two oxygen atoms cannot be joined to one another.
  • the number of carbon atoms gives the total number of carbon atoms contained in the radical.
  • a (C 3 -C 5 )-alkylene bridge is a carbon chain with three to five C atoms, this chain being bonded to the molecule in question via two different C atoms.
  • radicals just described can be mono- or polysubstituted with halogens and/or radicals containing N, O, P, S or Si atoms. These are particularly alkyl radicals of the type mentioned above having one or more of these heteroatoms in their chain or being bonded to the molecule via one of these heteroatoms.
  • (C 3 -C 8 )-Cycloalkyl means cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl radicals etc. These can be substituted with one or more halogens and/or radicals containing N, O, P, S or Si atoms and/or can have N, O, P or S atoms in the ring, such as e.g. 1-, 2-, 3-, 4-piperidyl, 1-, 2-, 3-pyrrolidinyl, 2-, 3-tetrahydrofuryl, 2-, 3-, 4-morpholinyl.
  • a (C 3 -C 8 )-cycloalkyl-(C 1 -C 8 )-alkyl radical refers to a cycloalkyl radical as set out above, which is bonded to the molecule via an alkyl radical as stated above.
  • (C 1 -C 8 )-Acyloxy within the framework of the invention means an alkyl radical as defined above with a maximum of 8 C atoms, which is bonded to the molecule via a COO-function.
  • (C 1 -C 8 )-Acyl within the framework of the invention means an alkyl radical as defined above with a maximum of 8 C atoms, which is bonded to the molecule via a CO— function.
  • a (C 6 -C 18 )-aryl radical is understood to mean an aromatic radical with 6 to 18 C atoms.
  • These include in particular compounds such as phenyl, naphthyl, anthryl, phenanthryl or biphenyl radicals, or systems of the type described above annelated to the molecule in question, such as e.g. indenyl systems, which can optionally be substituted with (C 1 -C 8 )-alkyl, (C 1 -C 8 )-alkoxy, NR 1 R 2 , (C 1 -C 8 )-acyl or (C 1 -C 8 )-acyloxy.
  • a (C 7 -C 19 )-aralkyl radical is a (C 6 -C 18 )-aryl radical bonded to the molecule via a (C 1 -C 8 )-alkyl radical.
  • a (C 3 -C 18 )-heteroaryl radical within the framework of the invention refers to a five-, six- or seven-membered aromatic ring system of 3 to 18 C atoms, which contains heteroatoms such as e.g. nitrogen, oxygen or sulfur in the ring.
  • radicals such as 1-, 2-, 3-furyl, such as 1-, 2-, 3-pyrrolyl, 1-, 2-, 3-thienyl, 2-, 3-, 4-pyridyl, 2-, 3-, 4-, 5-, 6-, 7-indolyl, 3-, 4-, 5-pyrazolyl, 2-, 4-, 5-imidazolyl, acridinyl, quinolinyl, phenanthridinyl and 2-, 4-, 5-, 6-pyrimidinyl are considered as such heteroaromatics.
  • a (C 4 -C 19 )-heteroaralkyl means a heteroaromatic system corresponding to the (C 7 -C 19 )-aralkyl radical.
  • Fluorine, chlorine, bromine and iodine are suitable as halogens (Hal).
  • PEG means polyethylene glycol
  • enantiomer-enriched or enantiomeric excess within the framework of the invention means the proportion of an enantiomer in a mixture with its optical antipode in a range of >50% and ⁇ 100%.
  • N-Acyl groups mean protective groups that are conventionally used in amino acid chemistry for the protection of nitrogen atoms. The following can be particularly mentioned in this capacity: formyl, acetyl, Moc, Eoc, phthalyl, Boc, Alloc, Z, Fmoc, etc.
  • membrane reactor means any reaction vessel in which the molecular weight-enlarged catalyst is enclosed in a reactor while low molecular weight substances are fed into the reactor or can leave it.
  • the membrane can be integrated directly into the reaction chamber or can be installed outside it in a separate filtration module, in which the reaction solution flows continuously or intermittently through the filtration module and the retentate is recycled into the reactor.
  • Suitable embodiments are described in WO98/22415 and in Wandrey et al. in Gonzbuch 1998, Maschinenstechnik und Chemieingenieuroch, VDI p. 151 ff.; Wandrey et al. in Applied Homogeneous Catalysis with Organometallic Compounds, Vol. 2, VCH 1996, p. 832 ff.; Kragl et al., Angew. Chem. 1996, 6, 684 f., among others.
  • a polymer-enlarged ligand/complex means one in which the molecular weight-enlarging polymer is covalently bonded to the ligand.
  • FIG. 1 shows a membrane reactor with dead-end filtration.
  • the substrate 1 is transferred via a pump 2 into the reactor chamber 3 , which has a membrane 5 .
  • the catalyst 4 in addition to the solvent, the catalyst 4 , the product 6 and unreacted substrate 1 are found.
  • Mainly low-molecular weight substances 6 are filtered off through the membrane 5 .
  • FIG. 2 shows a membrane reactor with cross-flow filtration.
  • the substrate 7 is transferred via the pump 8 into the agitated reactor chamber, in which solvent, catalyst 9 and product 14 are also found.
  • the pump 16 By means of the pump 16 a solvent flow is set up, which passes via an optionally present heat exchanger 12 into the cross-flow filtration cell 15 .
  • the low molecular-weight product 14 is separated off by means of the membrane 13 .
  • High molecular-weight catalyst 9 is then passed back into the reactor 10 with the solvent flow, optionally via a heat exchanger 12 again, optionally via the valve 11 .

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EP1490379B1 (de) 2010-05-19
HRP20040904A2 (en) 2004-12-31
CN1646547A (zh) 2005-07-27
CN1318433C (zh) 2007-05-30
DE10309356A1 (de) 2003-11-20
ATE468346T1 (de) 2010-06-15
BR0308970A (pt) 2005-01-11
US7589215B2 (en) 2009-09-15
US20070179301A1 (en) 2007-08-02
US20070123733A1 (en) 2007-05-31
JP2005529868A (ja) 2005-10-06
IL164342A0 (en) 2005-12-18
CA2481037A1 (en) 2003-10-16
EP1490379A1 (de) 2004-12-29
AU2003212297A1 (en) 2003-10-20
RU2004132221A (ru) 2005-09-10
WO2003084971A1 (en) 2003-10-16
KR20040097265A (ko) 2004-11-17
US7361786B2 (en) 2008-04-22

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