WO2004101581A2 - Nitrogen-containing monodentate phosphines and their use in catalysis - Google Patents

Nitrogen-containing monodentate phosphines and their use in catalysis Download PDF

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WO2004101581A2
WO2004101581A2 PCT/EP2004/004644 EP2004004644W WO2004101581A2 WO 2004101581 A2 WO2004101581 A2 WO 2004101581A2 EP 2004004644 W EP2004004644 W EP 2004004644W WO 2004101581 A2 WO2004101581 A2 WO 2004101581A2
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alkyl
aryl
group
mmol
radical
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PCT/EP2004/004644
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WO2004101581A3 (en
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Alexander Zapf
Mark Sundermeier
Ralf Jackstell
Matthias Beller
Thomas Riermeier
Axel Monsees
Uwe Dingerdissen
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Degussa Ag
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Priority to JP2006529728A priority Critical patent/JP4589329B2/en
Priority to CA002525890A priority patent/CA2525890A1/en
Priority to BRPI0410379-3A priority patent/BRPI0410379A/en
Priority to EP04730867.1A priority patent/EP1625133B1/en
Priority to US10/554,603 priority patent/US7589081B2/en
Publication of WO2004101581A2 publication Critical patent/WO2004101581A2/en
Publication of WO2004101581A3 publication Critical patent/WO2004101581A3/en
Priority to IL171943A priority patent/IL171943A0/en

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    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/023—Preparation; Separation; Stabilisation; Use of additives
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • 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
    • B01J31/2447—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 substituents on a ring of the condensed system or on a further attached ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/14—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D295/155—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
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    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6503—Five-membered rings
    • C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/828—Platinum

Definitions

  • the present invention relates to novel ligands for transition metals , to their preparation and to their use in catalytic reactions , especially for the improvement of haloaromatic compounds .
  • Haloaromatic compounds including especially chloroaromatic compounds, are intermediates which can be used variously in the chemical industry and which serve as preliminary products for the production of agricultural intermediates, pharmaceuticals, colourings, materials, etc.. Vinyl halides are also important intermediates which are used as starting materials for polymers and in the production of the above- mentioned products .
  • Palladium catalysts are generally advantageous, owing to the wide applicability of coupling substrates with in some cases good catalytic activities, while nickel catalysts have advantages in the field of the reaction of chloroaromatic compounds and vinyl chlorides. Moreover, nickel is more readily available than palladium.
  • Palladium and nickel catalysts used within the scope of the activation and further improvement of haloaromatic compounds are both palladium(II) and/or nickel ( II ) complexes as well as palladium(O) and/or nickel ( 0 ) complexes, although it is known that palladium(0) and nickel (0) compounds are the actual catalysts of the reaction, in particular, according to information in the literature, coordinatively unsaturated 14- and 16-electron palladiu ⁇ (O) and nickel (0) complexes stabilised with donor ligands such as phosphanes are formulated as the active species.
  • iodides When iodides are used as starting materials in coupling reactions it is also possible to dispense with phosphane ligands.
  • aryl iodides and vinyl iodides are starting materials which are scarcely available and therefore very expensive, and their reaction additionally yields stoichiometric amounts of iodine salt waste products.
  • other starting materials are used in the Heck reaction, such as aryl bromides or aryl chlorides, the addition of stabilising and activating ligands is necessary if catalytically effective reaction of the starting materials is to be possible.
  • More recent active catalyst systems are based on cyclopalladated phosphanes (W. A. Herrmann, C. BroEmer, K. Ofele, C.-P. Reisinger, T. Priermeier, M. Beller, H. Fischer, Angew. Chem. 1995, 107, 1989; Angew. Chem. Int . Ed. Engl . 1995, 34 , 1844) or mixtures of sterically demanding arylphosphanes (J. P. Wolfe, S. L. Buchwald, Angew. Chem. 1999, 111 , 2570; Angew. Chem. Int . Ed. Engl . 1999, 38, 2413) or tri-tert .
  • chloroaromatic compounds can generally not be activated in an industrially satisfactory manner even using these catalysts. Accordingly, in order to achieve high yields, comparatively large amounts of catalyst must be used. Therefore, despite all the further developments which have been made to catalysts in recent years, only a small number of industrial reactions of the arylation, carbonylation, olefination, etc. of chloroaromatic compounds have hitherto become known.
  • the object underlying the present invention was to provide novel ligands and catalysts which are suitable for large-scale applications, are readily accessible and convert chloro- and bromo- aromatic compounds as well as corresponding vinyl compounds to the respective coupling products in high yield and with high purity, with high catalyst productivity.
  • X independently of Y represents a nitrogen atom or a C-R 2 group
  • Y independently of X represents a nitrogen atom or a
  • R for each of the two R 1 groups independently of the other represents a radical selected from the group C ⁇ -C 24 -alkyl
  • C3-C 2 o-cycloalkyl which includes especially both monocyclic and also bi- and tri-cyclic cycloalkyl radicals
  • C 5 -Ci 4 -aryl which includes especially the phenyl, naphthyl, fluorenyl radical
  • radicals R 1 may themselves each be mono- or poly-substituted. These substituents, independently of one another, may be hydrogen, C ⁇ -C 2 o- alkyl, C 2 -C 20 -alkenyl, C 3 -C 8 -cycloalkyl, C 2 -C 9 -hetero- alkyl, C 5 -C ⁇ o-aryl, C 2 -C 9 -heteroaryl, wherein the number of hetero atoms, especially from the group N, 0, S, may be from 1 to 4, C ⁇ -C 2 n-alkoxy, preferably c ⁇ -C ⁇ o-alkoxy, particularly preferably OMe, C ⁇ -C ⁇ o-halo- alkyl, preferably trifluoromethyl, hydroxy, secondary, tertiary amino groups of the forms H- (C ⁇ -C 2 o-alkyl) , NH-(C 5 -Ci 0 -aryl) , N(C
  • R l 22 -R 9 represent a hydrogen, alkyl, alkenyl, cycloalkyl, aromatic or heteroaromatic aryl, O-alkyl, NH-alkyl, N- (alkyl) 2 , O-(aryl), NH-(aryl), N- (alkyl) (aryl) , O-CO- alkyl, O-CO-aryl, F, Si (alkyl) 3 , CF 3 , CN, C0 2 H, COH, S0 3 H, CONH 2 , CONH (alkyl) , CON(alkyl) , CON(alkyl) 2 , S0 2 (alkyl) , SO(alkyl), SO(aryl), S0 2 (aryl), S0 3 (alkyl), S0 3 (aryl), S-alkyl, S-aryl, NH-CO(alkyl) , C0 2 (alkyl), C0NH 2 , CO (alkyl) , N
  • alkyl represents a hydrocarbon radical having from 1 to 20 carbon atoms which may in each case be linear or branched
  • alkenyl represents a mono- or poly- unsaturated hydrocarbon radical having from 2 to 20 carbon atoms which may in each case be linear or branched
  • cycloalkyl represents a hydrocarbon having from 3 to 20 carbon atoms, wherein the alkyl, alkenyl and cycloalkyl groups may also carry further substituents as defined for R 1 .
  • Preferred substituents in this connection are selected from the group Br, Cl, F, (C ⁇ -C ⁇ 2 ) -alkyl, O- (C x -C ⁇ 2 ) -alkyl, phenyl, O-phenyl, NH( (C ⁇ -C ⁇ 2 ) -alkyl) , N( (C ⁇ -C ⁇ 2 ) -alkyl) 2 , and
  • aryl represents a 5- to 14-membered aromatic radical in which from one to four carbon atoms may also be replaced by hetero atoms from the group nitrogen, oxygen and sulfur so that a 5- to 14-membered hetero- aromatic radical is present and wherein the aryl or heteroaryl radical may carry further substituents as defined for R 1 , preferred substituents being selected from the group Br, Cl, F, (C ⁇ -C ⁇ 2 ) -alkyl, 0-(C!-C ⁇ 2 )- alkyl , phenyl , O-phenyl , NH 2 , NH ( (C ⁇ -C ⁇ 2 ) -alkyl ) , N((C ⁇ -C ⁇ 2 )-alkyl) 2 .
  • the mentioned alkyl radicals have preferably from 1 to 10 carbon atoms, particularly preferably from 1 to 5.
  • the alkenyl radicals have preferably from 2 to 10 carbon atoms, particularly preferably from 2 to 5.
  • the cycloalkyl radicals have preferably from 3 to 8 carbon atoms.
  • the aryl radicals have preferably from 6 to 10 carbon atoms, the heteroaryl radicals from 4 to 9.
  • radicals R 1 to R 9 are as defined above,
  • X is nitrogen and Y is a CR 9 group.
  • Preferred ligands of formula (I) or (II) carry at least one radical R 1 selected from the group consisting of phenyl, C ⁇ -C ⁇ o-alkyl , cyclopentyl, cyclohexyl, cycloheptyl, 1- adamantyl, 2-adamantyl, 5H-dibenzophospholyl, 9-phospha- bicyclo[3.3.1]nonanyl, 9-phosphabicyclo[4.2.ljnonanyl radicals .
  • Examples of preferred C ⁇ -C ⁇ o-alkyl radicals are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methyl- propyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2- ethylbutyl, 3-methylbutyl, 2, 2-dimethyIpropyl, 1-ethyl- propyl, n-hexyl, 1, 1-dimethyIpropyl, 1,2-dimethyIpropyl, 1- methylpentyl , 2-methylpentyl , 3-methylpentyl , 4-methyl- pentyl, 1,1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethyl- butyl, 2,2-dimethylbutyl, 2, 3-dimethylbutyl, 3, 3-dimethyl- butyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1,
  • Preferred radicals R 2 to R 9 are selected from the group hydrogen, C ⁇ -C ⁇ 0 -alkyl, C 2 -C ⁇ 0 -alkenyl, C ⁇ -C ⁇ o-haloalkyl, C3-C 8 -cycloalkyl, C ⁇ -Cio-aryl, which includes especially also phenyl, naphthyl, fluorenyl, and C 2 -C 6 -heteroaryl, wherein from 1 to 3 nitrogen atoms or an oxygen or sulfur atom may be present as hetero atom, and wherein two adjacent radicals R 2 to R 9 may be bridged with one another, there preferably being formed a 4- to 8- membered, preferably aromatic ring.
  • the ligands according to the invention can be prepared by reacting the corresponding phenylpyrrole derivative in the presence of a strong base, such as, for example, an alkyl- lithium compound, and subsequently adding a halophosphane, in accordance with the following reaction scheme, which is given by way of example
  • the novel phosphane ligands are used as catalysts in combination with transition metal complexes or transition metal salts of sub-group VIII of the periodic system of the elements, such as, for example, palladium, nickel, platinum, rhodium, iridium, ruthenium, cobalt.
  • the ligands according to the invention can generally be added in si tu to corresponding transition metal precursor compounds and accordingly used for catalytic applications.
  • transition metal compounds there are preferably used palladium or nickel compounds and particularly preferably palladium compounds .
  • the ligands according to the invention are generally added in si tu preferably to nickel (II) or palladium(II) salts or to nickel (II), palladium(II) or nickel (0) or palladium(O) complexes.
  • Preferred palladium complexes are, for example, palladium(II) acetate, palladium(II) chloride, palladium(II) bromide, lithium tetrachloropalladate(II) , palladiu (II) acetylacetonate, palladium(O) -dibenzylidene- acetone complexes, palladium(O) tetrakis (triphenyl- phosphane) , palladium(O) bis (tri-o-tolylphosphane) , palladium(II) propionate, palladium(II) bis (triphenyl- phosphane) dichloride, palladium (0) diallyl ether complexes, palladium(II) nitrate, palladium(II) chloride bis (acetonitrile) , palladium(II) chloride bis (benzo- nitrile) .
  • the phosphane ligand is generally used in excess relative to the transition metal.
  • the ratio of transition metal to ligand is preferably from 1:1 to 1:1000. Ratios of transition metal to ligand of from 1:1 to 1:100 are particularly preferred.
  • the exact transition metal/ligand ratio to be used depends on the concrete application, but also on the amount of catalyst used. Accordingly, it is generally customary to use low transition metal/ligand ratios at very low transition metal concentrations ( ⁇ 0.01 mol.%) than at transition metal concentrations of from 0.5 to 0.01 mol.% transition metal.
  • the catalysts are preferably used at temperatures of from 20 to 200°C; in many cases, it has proved advantageous to work at temperatures of from 30 to 180°C, preferably from 40 to 160°C.
  • the ligands can also be used without any loss of activity in reactions under pressure, reactions usually being carried out only up to a pressure of 100 bar, but preferably in the range of from normal pressure to 60 bar.
  • TON turnover rates
  • the transition metal is preferably used in a ratio of from 5 mol.% to 0.001 mol.%, particularly preferably from 0.5 mol.% to 0.01 mol.%, relative to the substrate.
  • phosphane ligands prepared in accordance with the invention have proved suitable especially as the ligand component for the catalytic preparation of arylated olefins
  • novel catalyst systems can also be used to catalyse other transition-metal-catalysed reactions, such as metathesis or hydrogenations of double bonds or carbonyl compounds, but especially palladium- and nickel-catalysed carbonylations of aryl halides, alkynylations using alkynes (Sonogashira couplings) , cross-couplings using organometallic reagents, such as, for example, zinc reagents or tin reagents .
  • a particular advantage of the ligands according to the invention is the high degree of activity induced by the ligands in the activation of readily available but inert chloroaromatic compounds.
  • the described catalyst and ligand systems can accordingly be used for large-scale purposes.
  • the phosphanes prepared in accordance with the invention can be used in the preparation of aryl olefins, dienes, diaryls, benzoic acid derivatives, acrylic acid derivatives, arylalkanes, alkynes, amines.
  • the compounds so prepared are used, for example, as UV absorbers, as intermediates for pharmaceuticals and agroche icals, as ligand precursors for metallocene catalysts, as perfumes, as active ingredients having biological activity and as structural units for polymers .
  • the hexane fractions are likewise transferred to the separating funnel.
  • the combined organic phases are washed with 15 ml of degassed water and dried over degassed sodium sulfate.
  • the solvents are distilled off and the viscous residue is dissolved in methanol with heating. After one day at room temperature, the mixture is cooled for four hours at 0°C.
  • the resulting white solid is filtered off and dried in vacuo (purity 90-95 %) .
  • PR X 2 PCy 2 72 % ( 3 J 1 1 P,-NMR -28.0 ppm) (Ll; N-PHOS-Cy)
  • PR 1 2 PPh 2 64 % ( 3 J 1 1 P,-NMR -29.8 ppm) (L2; N-PHOS-Ph)
  • Solution S-2 150 mmol. of 4-chloroanisole, 57 mmol. of tetradecane, 154 ml of abs. toluene
  • reaction metal pr-ecursor with ligand The following solutions are mixed under Ar and stirred for about 1 hour at room temperature (reaction metal pr-ecursor with ligand) :
  • a Vantage synthesizer is used to pipette the following amounts of the resulting solutions into the Vantage vials :
  • the Vantage vials so filled are heated for 4.0 hours at 110°C (Vantage setting) with shaking (1000 rpm) (heating phase 0.5 h/internal temperature about 120°C) .
  • the reaction is carried out as a one-pot reaction under protecting gas.
  • Working-up is carried out with 10 ml of each of methylene chloride and IN sodium hydroxide solution.
  • the reaction is monitored by means of GC, internal GC standard: hexadecane.
  • the mixture is then boiled for a further 1 hour at reflux, the solution is cooled, and 20 ml of degassed water are added thereto.
  • the organic phase is filtered off over magnesium sulfate.
  • the solution is concentrated in vacuo; 30 ml of pentane are added thereto, and the mixture is boiled for 1 hour at reflux.
  • the product precipitates in crystalline form at -30°C and is filtered off while cold. Yield: 2.48 g (65 %) .
  • the colour of the solution lightens to orange, and a white precipitate forms.
  • 30 ml of water are added to the mixture.
  • the orange organic phase is extracted 3 times using 20 ml of hexane each time.
  • the combined organic phases are washed with 10 ml of water and filtered over Na 2 S0 4 .
  • the solvent is removed in vacuo (45°C) .
  • the viscous orange residue is refluxed for 30 minutes in 30 ml of MeOH.
  • the product precipitates and is filtered off (1.1 g, 30 %) .
  • W-arylindole based ligand W-arylindole based ligand. ft-arylimidazole based ligand.
  • N-arylpyrrole or iV-arylindole or N- arylimidazole
  • TMEDA 15 mmol
  • n-BuLi 10 mmol, 1.6 M in hexane
  • the reaction mixture was refluxed for 3 h.
  • a solution of the corresponding chlorophosphine (10 mmol in 5 ml hexane) was slowly added via syringe. The mixture was further refluxed for lh.
  • a 30 mL pressure tube was loaded with Pd(OAc) 2 (0.025 mmol), the ligand (0.050 mmol), NaOtBu (6.0 mmol) and was purged by argon for 30 minutes. Then, were successively added under argon, toluene (5 mL) , the aryl chloride (5 mmol) and the amine (6 mmol) . The mixture was stirred under argon at 120 °C for 20 hours. After reaction, it was diluted with diethylether (15 mL) and washed with water (10 mL) .

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Abstract

The present invention relates to novel nitrogen-containing monodentate phosphane ligands of formula (I) and to their use in catalytic reactions, especially in the improvement of haloaromatic compounds.

Description

Nitrogen-containing monodentate phosphines and their use in catalysis
Description:
The present invention relates to novel ligands for transition metals , to their preparation and to their use in catalytic reactions , especially for the improvement of haloaromatic compounds .
Haloaromatic compounds, including especially chloroaromatic compounds, are intermediates which can be used variously in the chemical industry and which serve as preliminary products for the production of agricultural intermediates, pharmaceuticals, colourings, materials, etc.. Vinyl halides are also important intermediates which are used as starting materials for polymers and in the production of the above- mentioned products .
Catalysts which are frequently employed for the functionalisation of haloaromatic compounds or vinyl halides to aromatic olefins or dienes (Heck reaction,
Stille reaction), biaryls (Suzuki reaction), alkynes
(Sonogashira reaction) , carboxylic acid derivatives (Heck carbonylation) , amines (Buchwald-Hartwig reaction) are palladium catalysts and nickel catalysts. Palladium catalysts are generally advantageous, owing to the wide applicability of coupling substrates with in some cases good catalytic activities, while nickel catalysts have advantages in the field of the reaction of chloroaromatic compounds and vinyl chlorides. Moreover, nickel is more readily available than palladium.
Palladium and nickel catalysts used within the scope of the activation and further improvement of haloaromatic compounds are both palladium(II) and/or nickel (II) complexes as well as palladium(O) and/or nickel (0) complexes, although it is known that palladium(0) and nickel (0) compounds are the actual catalysts of the reaction, in particular, according to information in the literature, coordinatively unsaturated 14- and 16-electron palladiuπι(O) and nickel (0) complexes stabilised with donor ligands such as phosphanes are formulated as the active species.
When iodides are used as starting materials in coupling reactions it is also possible to dispense with phosphane ligands. However, aryl iodides and vinyl iodides are starting materials which are scarcely available and therefore very expensive, and their reaction additionally yields stoichiometric amounts of iodine salt waste products. If other starting materials are used in the Heck reaction, such as aryl bromides or aryl chlorides, the addition of stabilising and activating ligands is necessary if catalytically effective reaction of the starting materials is to be possible.
The catalyst systems described for olefinations, alkynylations , carbonylations, arylations, aminations and similar reactions frequently have satisfactory catalytic turnover numbers (TON) only with uneconomical starting materials such as iodoaromatic compounds and activated bromoaromatic compounds. Otherwise, in the case of deactivated bromoaromatic compounds and, especially, in the case of chloroaromatic compounds, large amounts of catalyst - usually more than 1 mol.% - must generally be added in order to achieve industrially usable yields (> 90 %) . Moreover, owing to the complexity of the reaction mixtures, simple recycling of the catalyst is not possible, so that recovery of the catalyst also gives rise to high costs, which generally stand in the way of industrial implementation. Furthermore, it is undesirable to work with large amounts of catalyst, especially when preparing active ingredients or preliminary products for active ingredients, because catalyst residues otherwise remain in the product in this case.
More recent active catalyst systems are based on cyclopalladated phosphanes (W. A. Herrmann, C. BroEmer, K. Ofele, C.-P. Reisinger, T. Priermeier, M. Beller, H. Fischer, Angew. Chem. 1995, 107, 1989; Angew. Chem. Int . Ed. Engl . 1995, 34 , 1844) or mixtures of sterically demanding arylphosphanes (J. P. Wolfe, S. L. Buchwald, Angew. Chem. 1999, 111 , 2570; Angew. Chem. Int . Ed. Engl . 1999, 38, 2413) or tri-tert . -butylphosphane (A. F. Littke, G. C. Fu, Angew. Chem. 1998, 110, 3586; Angew. Chem . Int . Ed. Engl . 1998, 37, 3387) with palladium salts or palladium complexes .
However, chloroaromatic compounds can generally not be activated in an industrially satisfactory manner even using these catalysts. Accordingly, in order to achieve high yields, comparatively large amounts of catalyst must be used. Therefore, despite all the further developments which have been made to catalysts in recent years, only a small number of industrial reactions of the arylation, carbonylation, olefination, etc. of chloroaromatic compounds have hitherto become known.
For the mentioned reasons, the object underlying the present invention was to provide novel ligands and catalysts which are suitable for large-scale applications, are readily accessible and convert chloro- and bromo- aromatic compounds as well as corresponding vinyl compounds to the respective coupling products in high yield and with high purity, with high catalyst productivity.
This object is achieved according to the invention by novel phosphane ligands of formula (I)
Figure imgf000005_0001
(0
wherein
X independently of Y represents a nitrogen atom or a C-R2 group and
Y independently of X represents a nitrogen atom or a
C-R ,9a group,
R for each of the two R1 groups independently of the other represents a radical selected from the group Cι-C24-alkyl,
C3-C2o-cycloalkyl, which includes especially both monocyclic and also bi- and tri-cyclic cycloalkyl radicals, C5-Ci4-aryl, which includes especially the phenyl, naphthyl, fluorenyl radical,
C2-Cι3-heteroaryl, wherein the number of hetero atoms, selected from the group N, 0, S, may be from 1 to 2, wherein the two radicals R1 may also be linked to one another, there preferably being formed a 4- to 8- membered saturated, unsaturated or aromatic ring.
The above-mentioned radicals R1 may themselves each be mono- or poly-substituted. These substituents, independently of one another, may be hydrogen, Cχ-C2o- alkyl, C2-C20-alkenyl, C3-C8-cycloalkyl, C2-C9-hetero- alkyl, C5-Cιo-aryl, C2-C9-heteroaryl, wherein the number of hetero atoms, especially from the group N, 0, S, may be from 1 to 4, Cι-C2n-alkoxy, preferably cι-Cιo-alkoxy, particularly preferably OMe, Cι-Cιo-halo- alkyl, preferably trifluoromethyl, hydroxy, secondary, tertiary amino groups of the forms H- (Cι-C2o-alkyl) , NH-(C5-Ci0-aryl) , N(Cι-C20-alkyl) 2, Nfd-Czo- alkyl) (C5-Ci0-aryl) , N(C5-Cι0-aryl) 2, N(Cι-C20- alkyl/C5-Cιo-aryl3)3 +, NH-CO-Cι-C20-alkyl, NH-CO-C5-C10- aryl, carboxylato of the forms COOH and COOQ (wherein Q represents either a monovalent cation or Ci-Cβ- alkyl) , Ci-Cβ-acyloxy, sulfinato, sulfonato of the forms S03H and S03Q (wherein Q represents either a monovalent cation, Cι-C2o-alkyl or C5-Cι0-aryl) , tri- Cι-C6-alkylsilyl, especially SiMe3, wherein two of the mentioned substituents may also be bridged with one another, there preferably being formed a 4- to 8-membered ring which can be further substituted preferably by linear or branched C1-C10- alkyl, C6-aryl, benzyl, Ci-Cio-alkoxy, hydroxy or benzyloxy groups .
R l22-R9 represent a hydrogen, alkyl, alkenyl, cycloalkyl, aromatic or heteroaromatic aryl, O-alkyl, NH-alkyl, N- (alkyl)2, O-(aryl), NH-(aryl), N- (alkyl) (aryl) , O-CO- alkyl, O-CO-aryl, F, Si (alkyl) 3, CF3, CN, C02H, COH, S03H, CONH2, CONH (alkyl) , CON(alkyl) 2, S02 (alkyl) , SO(alkyl), SO(aryl), S02(aryl), S03(alkyl), S03(aryl), S-alkyl, S-aryl, NH-CO(alkyl) , C02 (alkyl), C0NH2, CO (alkyl) , NHCOH, NHC02 (alkyl) , CO ( ryl) , C02<aryl) radical,
wherein two or more adjacent radicals, .each independently of the other (s), may also be linked to one another so that a condensed ring system is present and
wherein in R2 to R9 alkyl represents a hydrocarbon radical having from 1 to 20 carbon atoms which may in each case be linear or branched, alkenyl represents a mono- or poly- unsaturated hydrocarbon radical having from 2 to 20 carbon atoms which may in each case be linear or branched, and cycloalkyl represents a hydrocarbon having from 3 to 20 carbon atoms, wherein the alkyl, alkenyl and cycloalkyl groups may also carry further substituents as defined for R1. Preferred substituents in this connection are selected from the group Br, Cl, F, (Cι-Cι2) -alkyl, O- (Cx-Cι2) -alkyl, phenyl, O-phenyl, NH( (Cι-Cι2) -alkyl) , N( (Cι-Cι2) -alkyl) 2, and
aryl represents a 5- to 14-membered aromatic radical in which from one to four carbon atoms may also be replaced by hetero atoms from the group nitrogen, oxygen and sulfur so that a 5- to 14-membered hetero- aromatic radical is present and wherein the aryl or heteroaryl radical may carry further substituents as defined for R1, preferred substituents being selected from the group Br, Cl, F, (Cι-Cι2) -alkyl, 0-(C!-Cι2)- alkyl , phenyl , O-phenyl , NH2, NH ( (Cι-Cι2) -alkyl ) , N((Cι-Cι2)-alkyl)2.
The mentioned alkyl radicals have preferably from 1 to 10 carbon atoms, particularly preferably from 1 to 5. The alkenyl radicals have preferably from 2 to 10 carbon atoms, particularly preferably from 2 to 5. The cycloalkyl radicals have preferably from 3 to 8 carbon atoms. The aryl radicals have preferably from 6 to 10 carbon atoms, the heteroaryl radicals from 4 to 9.
Preference is given to ligands wherein X is CR2 and Y is CR9, yielding compounds of formula (II)
Figure imgf000008_0001
wherein the radicals R1 to R9 are as defined above, In a further preferred embodiment, X is nitrogen and Y is a CR 9 group.
Preferred ligands of formula (I) or (II) carry at least one radical R1 selected from the group consisting of phenyl, Cι-Cιo-alkyl , cyclopentyl, cyclohexyl, cycloheptyl, 1- adamantyl, 2-adamantyl, 5H-dibenzophospholyl, 9-phospha- bicyclo[3.3.1]nonanyl, 9-phosphabicyclo[4.2.ljnonanyl radicals . Examples of preferred Cι-Cιo-alkyl radicals are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methyl- propyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2- ethylbutyl, 3-methylbutyl, 2, 2-dimethyIpropyl, 1-ethyl- propyl, n-hexyl, 1, 1-dimethyIpropyl, 1,2-dimethyIpropyl, 1- methylpentyl , 2-methylpentyl , 3-methylpentyl , 4-methyl- pentyl, 1,1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethyl- butyl, 2,2-dimethylbutyl, 2, 3-dimethylbutyl, 3, 3-dimethyl- butyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1,2-trimethyIpropyl, 1,2,2-trimethylpropyl, 1-ethyl-l-methylpropyl, n-heptyl, n- octyl, n-nonyl, n-decyl, particular preference being given especially to the isopropyl radical and the tert. -butyl radical .
Preferred radicals R2 to R9 are selected from the group hydrogen, Cι-Cι0-alkyl, C2-Cι0-alkenyl, Cι-Cιo-haloalkyl, C3-C8-cycloalkyl, Cβ-Cio-aryl, which includes especially also phenyl, naphthyl, fluorenyl, and C2-C6-heteroaryl, wherein from 1 to 3 nitrogen atoms or an oxygen or sulfur atom may be present as hetero atom, and wherein two adjacent radicals R2 to R9 may be bridged with one another, there preferably being formed a 4- to 8- membered, preferably aromatic ring.
The ligands according to the invention can be prepared by reacting the corresponding phenylpyrrole derivative in the presence of a strong base, such as, for example, an alkyl- lithium compound, and subsequently adding a halophosphane, in accordance with the following reaction scheme, which is given by way of example
Figure imgf000009_0001
According to the invention, the novel phosphane ligands are used as catalysts in combination with transition metal complexes or transition metal salts of sub-group VIII of the periodic system of the elements, such as, for example, palladium, nickel, platinum, rhodium, iridium, ruthenium, cobalt. The ligands according to the invention can generally be added in si tu to corresponding transition metal precursor compounds and accordingly used for catalytic applications. However, it may occasionally be advantageous for specific mono-, di-, tri- or tetra- phosphane complexes of the mentioned transition metals to be prepared first and subsequently used for catalysis reactions. The catalytic activity can thereby be increased further in some catalyst systems.
As transition metal compounds there are preferably used palladium or nickel compounds and particularly preferably palladium compounds .
The ligands according to the invention are generally added in si tu preferably to nickel (II) or palladium(II) salts or to nickel (II), palladium(II) or nickel (0) or palladium(O) complexes. Preferred palladium complexes are, for example, palladium(II) acetate, palladium(II) chloride, palladium(II) bromide, lithium tetrachloropalladate(II) , palladiu (II) acetylacetonate, palladium(O) -dibenzylidene- acetone complexes, palladium(O) tetrakis (triphenyl- phosphane) , palladium(O) bis (tri-o-tolylphosphane) , palladium(II) propionate, palladium(II) bis (triphenyl- phosphane) dichloride, palladium (0) diallyl ether complexes, palladium(II) nitrate, palladium(II) chloride bis (acetonitrile) , palladium(II) chloride bis (benzo- nitrile) .
In catalytic applications, the phosphane ligand is generally used in excess relative to the transition metal. The ratio of transition metal to ligand is preferably from 1:1 to 1:1000. Ratios of transition metal to ligand of from 1:1 to 1:100 are particularly preferred. The exact transition metal/ligand ratio to be used depends on the concrete application, but also on the amount of catalyst used. Accordingly, it is generally customary to use low transition metal/ligand ratios at very low transition metal concentrations (< 0.01 mol.%) than at transition metal concentrations of from 0.5 to 0.01 mol.% transition metal.
The catalysts are preferably used at temperatures of from 20 to 200°C; in many cases, it has proved advantageous to work at temperatures of from 30 to 180°C, preferably from 40 to 160°C. The ligands can also be used without any loss of activity in reactions under pressure, reactions usually being carried out only up to a pressure of 100 bar, but preferably in the range of from normal pressure to 60 bar.
When carrying out catalytic reactions using ligands of formula (I) , high turnover rates (TON) can be achieved with a low catalyst concentration. The transition metal is preferably used in a ratio of from 5 mol.% to 0.001 mol.%, particularly preferably from 0.5 mol.% to 0.01 mol.%, relative to the substrate.
The phosphane ligands prepared in accordance with the invention have proved suitable especially as the ligand component for the catalytic preparation of arylated olefins
(Heck reactions) , biaryls (Suzuki reactions) , α-aryl ketones and amines from aryl halides or vinyl halides.
However, it is obvious to the person skilled in the art that the novel catalyst systems can also be used to catalyse other transition-metal-catalysed reactions, such as metathesis or hydrogenations of double bonds or carbonyl compounds, but especially palladium- and nickel-catalysed carbonylations of aryl halides, alkynylations using alkynes (Sonogashira couplings) , cross-couplings using organometallic reagents, such as, for example, zinc reagents or tin reagents .
A particular advantage of the ligands according to the invention is the high degree of activity induced by the ligands in the activation of readily available but inert chloroaromatic compounds. The described catalyst and ligand systems can accordingly be used for large-scale purposes.
The phosphanes prepared in accordance with the invention can be used in the preparation of aryl olefins, dienes, diaryls, benzoic acid derivatives, acrylic acid derivatives, arylalkanes, alkynes, amines. The compounds so prepared are used, for example, as UV absorbers, as intermediates for pharmaceuticals and agroche icals, as ligand precursors for metallocene catalysts, as perfumes, as active ingredients having biological activity and as structural units for polymers .
Implementation Examples :
General
Reactions of compounds sensitive to air were carried out in an argon-filled glove-box or in standard Schlenk tubes. The solvents tetrahydrofuran (THF) , diethyl ether and dichloromethane were degassed and rendered absolute by means of a solvent-drying installation (Innovative Technologies) by filtration through a column packed with activated aluminium oxide. Toluene and pentane were additionally freed of oxygen using a column packed with a copper catalyst.
The Examples which follow serve to explain the invention without limiting it thereto.
Preparation of ligands 1 to 3 (Ll to L3) :
10 mmol. of phenylpyrrole are dissolved under argon in 20 ml of absolute hexane. 10 mmol. of TMEDA and 10 mmol. of n-BuLi (1.6 M in hexane) are added at room temperature. After three hours' heating under reflux, a yellow suspension is obtained. It is cooled to room temperature, and 10 mmol. of C1-PR1 2 are slowly added thereto. After reacting for one hour under reflux, hydrolysis is carried out at room temperature using 15 ml of degassed water. The organic phase is transferred to a separating funnel, under argon, with the aid of a cannula. The aqueous phase is extracted twice using 15 ml of hexane each time. The hexane fractions are likewise transferred to the separating funnel. The combined organic phases are washed with 15 ml of degassed water and dried over degassed sodium sulfate. The solvents are distilled off and the viscous residue is dissolved in methanol with heating. After one day at room temperature, the mixture is cooled for four hours at 0°C. The resulting white solid is filtered off and dried in vacuo (purity 90-95 %) .
Yields:
PRX 2 = PCy2 72 % ( 3J11P,-NMR -28.0 ppm) (Ll; N-PHOS-Cy) PR12 = PPh2 64 % ( 3J11P,-NMR -29.8 ppm) (L2; N-PHOS-Ph)
31, PRX 2 = PtBu2 40 % ("P-NMR 3.6 ppm) (L3; N-PHOS-cBu)
Catalysis Examples 1 to 32 : Suzuki couplings
1.25 mmol. of phenylboronic acid and 2.00 mmol. of base are weighed into 2.5 ml glass bottles . These bottles are purged with argon and sealed. All further stock solutions are prepared under argon.
Solution S-l: 147 mmol. of 2-chlorotoluene, 58 mmol. of tetradecane, 155 ml of abs. toluene
Solution S-2: 150 mmol. of 4-chloroanisole, 57 mmol. of tetradecane, 154 ml of abs. toluene
Solution M-l: 0.073 mmol. pd of palladiu (II) acetate, 49 ml of abs . toluene
Solution M-2 0.065 mmol.p of tris- (dibenzylideneacetone) - dipalladium(O) , 49 ml of abs. toluene
Solution L-1: 0.04 mmol. of N-PHOS-Cy (Ll) , 10 abs. toluene Solution L-2: 0.08 mmol. of N-PHOS-tBu (L3), 21 abs. toluene
The following solutions are mixed under Ar and stirred for about 1 hour at room temperature (reaction metal pr-ecursor with ligand) :
Figure imgf000014_0001
A Vantage synthesizer is used to pipette the following amounts of the resulting solutions into the Vantage vials :
1. 1.25 ml of S-l (No. 1-8), (No. 17-24) 1.25 ml of S-2 (No. 9-16), (No. 25-32)
1.25 ml of M-L-l (No. 1-16) or 1.25 ml of M-L-2 (No. 17-32) .
Using the Vantage mixing/heating unit, the Vantage vials so filled are heated for 4.0 hours at 110°C (Vantage setting) with shaking (1000 rpm) (heating phase 0.5 h/internal temperature about 120°C) .
After the reaction, 1.0 ml of each reaction solution is filtered over silica gel. The solution so obtained is analysed by means of GC. The yields of the individual conversions are summarised in Table 1.
Table 1: Summary of the results of Catalysis Examples 1 to 32
Figure imgf000015_0001
Figure imgf000016_0001
Catalysis Examples 33 to 59:
Suzuki reaction of aryl chlorides with phenylboronic acid/- pyrrolylphosphanes
R-Ar-Cl + PhB(OH)2 → R-Ar-Ph
Reagents: 3 mmol. of ArCl, 4.5 mmol. of PhB(OH)2, 6 mmol. of K3P04, Pd(OAc)2, Pd/L = 1:2, 6 ml of toluene, 20 hours. The reaction is carried out as a one-pot reaction under protecting gas. Working-up is carried out with 10 ml of each of methylene chloride and IN sodium hydroxide solution. The reaction is monitored by means of GC, internal GC standard: hexadecane.
The starting materials used and the results of the conversions are summarised in Table 2.
Table 2: Summary of the results of Catalysis Examples 33 to 59
Figure imgf000016_0002
Figure imgf000017_0001
a) unknown (not visible in the GC) decomposition products. Both starting material and product withstand the basic working-up undamaged. Decomposition (> 60 %) but scarcely any product (< 10 %) is observed even at a reaction temperature of 60°C. Examples 60 to 64: Examples of ligand syntheses
Example 60: Synthesis of W-phenyl-2- (di-l-adamantyl- phosphino) pyrrole
T EDA, BuLi hexane
Figure imgf000018_0001
Figure imgf000018_0002
1.6 ml of TMEDA (15 mmol.) are added to a suspension of 1.43 g (10 mmol.) of N-phenylpyrrole in 30 ml of hexane. 6.25 ml of 1.6 molar n-butyllithium solution (10 mmol.) are added at room temperature. The mixture is then heated for 2.5 hours at reflux temperature (solution 1). In another flask, 3.36 g (10 mmol.) of di-1-adamantylchlorophosphane are mixed with 40 ml of hexane and heated to 76°C (solution 2) . The boiling solution 1 is then slowly transferred into solution 2, which is at 76°C, by means of a cannula. The mixture is then boiled for a further 2 hours at reflux, the solution is cooled, and 20 ml of water are added thereto. The organic phase is filtered off over magnesium sulfate. The solution is concentrated in vacuo; 15 ml of toluene are added thereto, and the mixture is heated to 60°C and then cooled. After one day at room temperature, the product is filtered off. Yield: 3.3 g (75 %) .
31P NMR (161 MHz, CDC13) : 5 = -4.5. H NMR (400 MHz, CDCI3) : δ = 1.7 (bs, 16H) , 1.7-2.0 (m, 22H) , 6.4 (dd, Ji = 8.6, 12.8, J2 = 3.5, 1H) , 6.75 (dd, J = 3.5, J2 = 1, 1H) , 6.9-7.0 (m, 1H) , 7.25-7.3 (m, 2H) , 7.35-7.45 (m, 3H) .
13C NMR (100.6 MHz, CDCI3) : 5 = 28.6 (d, JPC = 11.5), 37, 37.5 (d, JpC = 17.2), 41.6 (d, JPC = 11.5), 108.2, 119.5 (d, JPC = 4 . 7 ) , 125 . 8 , 126 (d, JPC = 10 . 8 ) , 127 .3 , 128 . 2 ,
128.3 (d, jpC = 3.8), 141.6 (d, JPC = 1.9).
MS: m/z (%) : 443 (68), 308 (13), 172 (14), 135 (100), 107
(7), 93 (19), 79 (17) . HRMS: C30H38NP: calc. 443.2742; found 443.26775.
Example 61: Synthesis of l-mesityl-2- (dicyclohexyl- phosphino) imidazole
Figure imgf000019_0001
1.6 ml of TMEDA (15 mmol.) are added to a suspension of 1.86 g (10 mmol.) of N-mesitylimidazole in 30 ml of hexane. 6.25 ml of 1.6 molar n-butyllithium solution (10 mmol.) are added at room temperature. The mixture is then heated for 2.5 hours at reflux temperature (solution 1). In another flask, 2.2 ml (10 mmol.) of dicyclohexylchlorophosphane are mixed with 20 ml of hexane and heated to 60°C (solution 2) . The boiling solution 1 is then slowly transferred into solution 2, which is at 60°C, by means of a cannula. The mixture is then boiled for a further 1 hour at reflux, the solution is cooled, and 20 ml of degassed water are added thereto. The organic phase is filtered off over magnesium sulfate. The solution is concentrated in vacuo; 30 ml of pentane are added thereto, and the mixture is boiled for 1 hour at reflux. The product precipitates in crystalline form at -30°C and is filtered off while cold. Yield: 2.48 g (65 %) .
31 P NMR (161 MHz, CDC13) : δ = -18.9 ^ NMR (400 MHz, CDC13): δ = 0.9-1.2 (m, 11H) , 1.5-1.7 (m, 11H), 1.9 (s, 6H) , 1.9-2.0 (m, 2H) , 2.2 (s, 3H) , 6.8-6.9 (m, 3H), 7.3 (s, 1H) .
13C NMR (100.6 MHz, CDC13) : δ = 18.5, 20.9, 26.9, 27.5, 27.7 (d, J = 9.5), 30.4 (d, J = 14.3), 30.9 (d, J = 10.5), 34.6 (d, J = 9.5), 122.7, 129.2, 131.5, 134.9, 135.5, 138.2, 147.5 (d, J = 16.2) .
MS: m/z (%): 382 (11), 299 (100), 217 (24), 202 (7), 185 (27), 83 (7) , 55 (21) .
Example 62: Synthesis of N- (2-methoxyphenyl) -2- (dicyclo- hexylphosphino) pyrrole
a) Synthesis of N- (2-methoxyphenyl)pyrrole
Figure imgf000020_0001
liquid
Figure imgf000020_0002
Lit.: Faigl, F.; Fogassy, K. Thuner, A. Toke, L. Tetrahedron 1997, 53 , 4883.
10.95 g (83 mmol.) of 1 and 4.7 g (38 mmol.) of 2 are refluxed for 2 hours in 10 ml of glacial acetic acid. The colour of the solution changes from yellow through red to black. The mixture is then diluted with 75 ml of distilled water and extracted twice with 100 ml of CH2C12. Na2C03 is added to the black organic solutions . After filtration and concentration (20 mbar, 50°C) , a black oil is obtained and is distilled in vacuo. Yield: 4.45 g (25.7 mmol.; 75 %) . XH NMR (25°C, CDCI3): δ (ppm) = 3.8 (s, 3H) , 6.3 (t, J = 2.2 Hz, 2H) , 7.0 (m, 4H) , 7.3 (m, 2H) . b) Synthesis of N- ( 2 -methoxyphenyl ) -2- (dicyclohexyl- phosphino) pyrrole
Figure imgf000021_0001
beige solid
0) 30 %
3.14 ml (15 mmol.) of N, N,
Figure imgf000021_0002
triamine (PMDTA) are added to a solution of 1.73 g (10 mmol.) of 1 in 30 ml of hexane. A solution (1.6 M in hexane) of n-BuLi (6.25 ml, 10 mmol.) is added dropwise. After 3 hours under reflux (75°C) , the colour of the solution has changed from yellow to black. Without cooling this mixture, 2.2 ml (10 mmol.) of chlorodicyclohexyl- phosphane dissolved in 20 ml of hexane are added dropwise. Refluxing is carried out for a further one hour. The colour of the solution lightens to orange, and a white precipitate forms. After cooling to room temperature, 30 ml of water are added to the mixture. The orange organic phase is extracted 3 times using 20 ml of hexane each time. The combined organic phases are washed with 10 ml of water and filtered over Na2S04. The solvent is removed in vacuo (45°C) . The viscous orange residue is refluxed for 30 minutes in 30 ml of MeOH. On cooling to RT, the product precipitates and is filtered off (1.1 g, 30 %) . lE NMR (25°C, C6D6) : δ (ppm) = 1.1-1.9 (m, 22H) , 3.2 (s, 3H) , 7.0 (m, 4H) , 6.5-7.2 (m, 3H) .
13C NMR (25°C, C6D6) : δ (ppm) = 27.2, 27.7, 27.8, 29.6, 30.9, 34.9, 55.1, 109.8, 111.8, 116.5, 116.6, 120.2, 123.6, 129.3, 130.9, 136.3, 156.0. 31P NMR (25°C, C6D6) : δ (ppm) = -26.8. Example 63 : Synthesis of 2\7-phenyl-2- (dicyclohexyl- phosphino) indole
a) Synthesis of N-phenyl indole
Figure imgf000022_0001
(3)
(2) yellow liquid l eq. 1.5 eq. 75 %
Lit.: Synthesis: Klapars, A.; Antilla, J.; Huang, X. ; Buchwald, S. j. Am. Chem. Soc . 2001, 123 , 7727. Analysis: (a) Nishio, T. J. Org. Chem. 1988, 53 , 1323. (b) Beller, M. ; Breindl, C; Riermeier, T. ; Tillack, A. J. Org. Chem. 2001, 66, 1403.
0.19 g (0.1 mmol.) of Cul, 2.34 g (20 mmol.) of 1, 8.82 g (42 mmol.) of K3P04, 0.48 ml (4 mmol.) of 1, 2-diaminocyclo- hexane and 3.16 ml (30 mmol.) of 2 are stirred for 24 hours at 110°C in 20 ml of dry dioxane. The mixture is then diluted with 50 ml of ethyl acetate. The violet precipitate is filtered off over silica gel, yielding a yellow solution, which is concentrated in vacuo (20 mbar, 50°C) . The orange oil that remains is purified by column chromatography (silica gel, hexane/ethyl acetate 98/2) . Yield: 3.0 g (15.5 mmol.; 75 %) . λH NMR (25°C, CDCI3): δ (ppm) = 6.45 (m, 1H) , 6.9-7.5 (m, 10H) . 13
C NMR (25°C, CDC13) : δ (ppm) = 104.1, 111.1, 120.9, 121.7, 122.9, 124.9, 126.9, 128.5, 129.9, 130.1, 130.6, 132.1, 136.4, 140.3.
b) Synthesis of itf-phenyl-2- (dicyclohexylphosphino) indole
TMEDA. BuLi
hexane, 75 °C.2h
Figure imgf000023_0001
Figure imgf000023_0002
white solid
(1) 17%
1.6 ml (15 mmol.) of TMEDA are added to 1.93 g (10 mmol.) of 1 in 30 ml of hexane. A solution (1.6 M in hexane) of n- BuLi (6.25 ml, 10 mmol.) is added dropwise. After 3 hours' reflux (75°C) , the colour has deepened from yellow to orange. Without cooling, a solution of 2.2 ml (10 mmol.) of chlorodicyclohexylphosphane in 20 ml of hexane is added dropwise. Refluxing is carried out for a further one hour, the colour of the mixture lightening again and a white solid precipitating. After cooling, 30 ml of water are added to the mixture. The aqueous phase is extracted 3 times using 20 ml of hexane each time. The combined organic phases are washed with 10 ml of water, dried over Na2S04 and concentrated in vacuo (45°C) . The yellow residue is boiled for 30 minutes in 30 ml of MeOH. After cooling to RT, the resulting product is filtered off (660 mg, 17 %) . 31P NMR (25°C, C6D6) : δ (ppm) = -24.8. Example 64: Synthesis of N- (naphthyl) -2- (dicyclohexyl- phosphino ) pyrrole
a) Synthesis of itf-naphthylpyrrole
Figure imgf000024_0001
(2) (11 (3) 1 eq. 2eq. pink crystals
50%
Lit.: Analysis: (a) Paredes, E.; Biolatto, B.; Kneeteman, M. ; Mancini, P. Tetrahedron Lett. 2000, 41, 8079. (b) Gross, H. Chem. Ber. 1962, 95, 2270.
10.95 g (83 mmol.) of 1 are added to a violet solution of 5.44 g (38 mmol.) of 2 in 10 ml of glacial acetic acid. The resulting brown solution is refluxed for 3 hours under argon (120°C) , whereupon its colour changes to black. The solution is concentrated to half the volume in vacuo (20 mbar, 50°C) before being hydrolysed with 20 ml of water. The organic phase is extracted with CH2CI2 (3 x 30 ml), dried over Na2S04 and concentrated (20 mbar, 50°C) , there being obtained a black oil which is purified by column chromatography (silica gel, hexane/ethyl acetate 85/15). Yield: 3.53 g (18.3 mmol.) of a red oil which crystallises at -25°C (pink crystals) .
XH NMR (25°C, CDCI3) : δ (ppm) = 6.3 (t, J = 2.2 Hz, 2H) , 6.7 (t, J = 2.2 Hz, 2H) , 6.9-7.2 (m, 4H) , 7.3 (d, 8.1 Hz, 1H) , 7.4 (d, 8.1 Hz, 1H) , 7.7 (d, 8.1 Hz, 1H) .
13C NMR (25°C, CDC13) : δ (ppm) = 110.0, 123.6, 123.8, 123.9, 125.7, 126.9, 127.4, 128.2, 130.7, 134.9, 139.0. Elemental analysis: found (%) C 86.7 (th: 87.0), H 5.89 (5.70), N 7.29 (7.30) . b) Synthesis of N- (naphthyl) -2- (dicyclohexylphosphino) pyrrole
PMDTA, BuLi
hexane, 75 °C, 2h
Figure imgf000025_0002
Figure imgf000025_0001
yellow solid
(I) 24 %
1.6 ml (15 mmol.) of TMEDA are added to a solution of 1.93 g (10 mmol.) of 1 in 30 ml of hexane. A solution (1.6 M in hexane) of n-BuLi (6.25 ml, 10 mmol.) is added dropwise. After 3 hours' reflux (75°C) , the colour has changed from orange through green to black. Without cooling, a solution of 2.2 ml (10 mmol.) of chlorodicyclo- hexylphosphane in 20 ml of hexane is added dropwise and refluxing is carried out for a further one hour. The colour of the solution changes to yellow, and a white precipitate forms. After cooling to RT, 30 ml of water are added to the mixture. The aqueous phase is extracted 3 times using 20 ml of hexane each time. The combined organic phases are washed with 10 ml of water, dried over Na2S04 and concentrated in vacuo (45°C) . The orange oil that remains is refluxed for 30 minutes in 30 ml of MeOH (60°C) . On cooling to -25°C, the product precipitates in the form of a yellow solid and is filtered off (0.9 g, 24 %) . 31P NMR (25°C, C6D6) : δ (ppm) = -23.3. Example 65 : ligands
Figure imgf000026_0001
W-arylpyrrole based ligand.
Figure imgf000026_0002
13 (10)
Figure imgf000026_0003
W-arylindole based ligand. ft-arylimidazole based ligand.
General procedure:
In a three nacked 100 ml round bottom flask with reflux condenser, N-arylpyrrole (or iV-arylindole or N- arylimidazole) (10 mmol) was dissolved in 20 ml of freshly distilled n-hexane under argon. TMEDA (15 mmol) was added followed by n-BuLi (10 mmol, 1.6 M in hexane) at room temperature. The reaction mixture was refluxed for 3 h. A solution of the corresponding chlorophosphine (10 mmol in 5 ml hexane) was slowly added via syringe. The mixture was further refluxed for lh. After cooling to room temperature, degassed water (15 ml) was added and the mixture was stirred to get a clear solution. The aqueous layer was extracted with hexane (2x 15 ml) and the combined organic layers were washed with degassed water (15 ml) . The solution was dried over Na2S04 and concentrated at 45 °C to get a viscous liquid which was recrystallized from methanol or toluene.
Example 66 : Catalytic amination of aryl chlorides
A 30 mL pressure tube was loaded with Pd(OAc)2 (0.025 mmol), the ligand (0.050 mmol), NaOtBu (6.0 mmol) and was purged by argon for 30 minutes. Then, were successively added under argon, toluene (5 mL) , the aryl chloride (5 mmol) and the amine (6 mmol) . The mixture was stirred under argon at 120 °C for 20 hours. After reaction, it was diluted with diethylether (15 mL) and washed with water (10 mL) . After extraction, the organic phase was dried over MgS04, concentrated under vacuum and the final product was isolated by column chromatography (silicagel, hexane/ethyl acetate 90/10) . Alternatively, diethyleneglycol-di-n- butylether or hexadecane was added as internal standard, and quantitative analysis was done by gas chromatography.
Table 1: Amination of chloro-benzene with aniline using ligands 1 to 10: comparison of the activity.
Entry Ligand Conv. [%] [a] Yield [%][ ] T.O.N
Figure imgf000029_0001
Figure imgf000030_0001
10 C N PAd2 49 46 92
-
5 mmol aryl chloride, 6 mmol amine, 6 mmol NaOtBu, 0.5 mol% Pd(OAc)2, 1 mol% ligand, 5 mL toluene, 48 h, 120 °C, [a] Average of 2 runs, determined by GC using diethyleneglycol di-n-butyl ether as internal standard.
Table 2: Various aminations of chloro-benzene using ligand 9.
_ . Aryl , . , Conv. Yield
Entry chloride ^ ne Pr°dUCt [%][al [%][a]
° *o σsX) 94 87
Figure imgf000030_0002
° -So α;O 100 94
Figure imgf000031_0001
5 mmol aryl chloride, 6 mmol amine, 6 mmol NaOtBu, 0.5 mol% Pd(OAc)2, 1 mol% ligand, 5 mL toluene, 20 h, 120 °C. Reaction time has not been minimized, [a] Average of 2 runs, determined by GC using diethyleneglycol di-n-butyl ether or hexadecane as internal standard, [b] The reaction was conducted within 48 hours, [c] Ligand 5 was used (2 equiv/Pd) .
Table 3: Various aminations of functionalized aryl-chlorides and chloro-pyridines using ligand 9.
Aryl- , . _ , Conv. Yield chloride Amine ProduCt [%]ta] [%][a]
Figure imgf000031_0002
Figure imgf000031_0003
Figure imgf000031_0004
Figure imgf000031_0005
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000033_0002
Figure imgf000033_0003
5 mmol aryl chloride, 6 mmol amine, 6 mmol NaOtBu, 0.5 mol% Pd(OAc)2, 1 mol% ligand, 5 mL toluene, 20 h, 120 °C. Reaction time has not been minimized, [a] Average of 2 runs, determined by GC using diethyleneglycol di-n-butyl ether or hexadecane as internal standard, [b] 1 mol% Pd(OAc)2, 2 mol% ligand.
Table 4: Amination of 3-chloro-toluene with W-methyl- aniline: variations of temperature and catalyst loading iErnntt-wry ,»n.o!l,%, «Pdj
Figure imgf000034_0001
T[eβm<pJ]. C[o%n]vM. Y[%ie]ltad] „TO_„N
1 0.5 2 120 100 95 190
2 0.5 2 100 100 92 184
3 0.5 2 80 100 90 180
4 0.5 2 60 100 89 178
5 0.5 2 40 100 90 180
6 0.25 2 120 100 91 364
7 0.1 2 120 98 86 860
8 0.05 2 120 83 73 1460
9 0.025 2 120 70 62 2480
10 0.025 10 120 78 67 2680
11 0.01 2 120 24 23 2300
12 0.01 25 120 39 33 3300
13 0.01 50 120 45 37 3700
5 mmol aryl chloride, 6 mmol amine, 6 mmol NaOtBu, 5 mL toluene, 20 h. Reaction time has not been minimized, [a] Average of 2 runs, determined by GC using diethyleneglycol di-n-butyl ether as internal standard. Table 5: Various aminations of aryl-chlorides at low temperature using ligand 9.
Entry / r1" Amine chloride Product Temp. Yield [°C] [%]lal
Figure imgf000035_0001
Figure imgf000035_0002
Figure imgf000035_0003
5 mmol aryl chloride, 6 mmol amine, 6 mmol NaOtBu, 0.5 mol% Pd(OAc)2, 1 mol% ligand, 5 mL toluene, 20 h. Reaction time has not been minimized, [a] Average of 2 runs, determined by GC using diethyleneglycol di-n-butyl ether or hexadecane as internal standard, [b] 1 mol% Pd(OAc)2/ 2 mol% ligand.

Claims

Patent claims :
1 . Phosphane ligands of formula ( I )
Figure imgf000036_0001
(0 wherein
independently of Y represents a nitrogen atom or a C-R2 group and independently of X represents a nitrogen atom or a C-R9 group,
for each of the two R1 groups independently of the other represents a radical selected from the group
Cι-C24-alkyl,
C3-C2o-cycloalkyl, which includes especially both monocyclic and also bi- and tri-cyclic cycloalkyl radicals,
Cδ-Ci4-aryl, which includes especially the phenyl, naphthyl, fluorenyl radical,
C2-Ci3-heteroaryl, wherein the number of hetero atoms, selected from the group N, 0, S, may be from 1 to 2,
wherein the two radicals R1 may also be linked to one another, and wherein the above-mentioned radicals R1 may themselves each be mono- or poly-substituted independently of one another by substituents selected from the group hydrogen, Cι-C2o-alkyl, C2-C2o-alkenyl, C3-C8-cycloalkyl, C2-C9-hetero- alkyl, C5-Cι0-aryl, C2-C9-heteroaryl, wherein the number of hetero atoms from the group N, 0, S may be from 1 to 4, Cι-C20-alkoxy, Cι-Cι0-haloalkyl, hydroxy, amino of the forms NH- (Cχ-C2o-alkyl) , NH- (Cs-Cio-aryl), N(Cι-C20-alkyl)2, N(Cι-C20- alkyl) (Cs-Cio-aryl) , N<C5-Cιo-aryl)2, N(Cι-C20- alkyl/C5-Cιo-aryl3)3 +, NH-CO-C1-C20-alkyl, NH-CO- Cs-Cio-aryl, carboxylato of the forms COOH and COOQ (wherein Q represents either a monovalent cation or Ci-Cβ-alkyl) , Ci-Cβ-acyloxy, sulfinato, sulfonato of the forms SO3H and SO3Q (wherein Q represents either a monovalent cation, C1-C20- alkyl or Cs-Cio-aryl) , tri-Cι-C6-alkylsilyl, wherein two of the mentioned substituents may also be bridged with one another,
R2-R9 represent a hydrogen, alkyl, alkenyl, cycloalkyl, aromatic or heteroaromatic aryl, O-alkyl, NH- alkyl, N- (alkyl) 2, O-(aryl), NH-(aryl), N- (alkyl) (aryl) , 0-CO-alkyl, O-CO-aryl, F,
Si (alkyl) 3, CF3, CN, C02H, COH, SO3H, CONH2, CONH(alkyl), CON(alkyl)2, S02(alkyl), SO(alkyl), SO (aryl), S02(aryl), S03 (alkyl), S03(aryl), S- alkyl, S-aryl, NH-CO (alkyl) , C02 (alkyl), CONH2, CO (alkyl), NHCOH, NHC02 (alkyl) , CO (aryl),
C02 (aryl) radical ,
wherein two or more adjacent radicals, each independently of the other (s), may also be linked to one another so that a condensed ring system is present and wherein in R2 to R9 alkyl represents a hydrocarbon radical having from 1 to 20 carbon atoms which may in each case be linear or branched, alkenyl represents a mono- or poly- unsaturated hydrocarbon radical having from 2 to 20 carbon atoms which may in each case be linear or branched, cycloalkyl represents a hydrocarbon having from 3 to 20 carbon atoms, aryl represents a 5- to 14- membered aromatic radical, wherein from one to four carbon atoms in the aryl radical may also be replaced by hetero atoms from the group nitrogen, oxygen and sulfur so that a 5- to 14-membered heteroaromatic radical is present, wherein the radicals R2 to R9 may also carry further substituents as defined for R1.
2. Ligands according to claim 1, characterised in that X represents a CR2 group and Y represents a CR9 group.
3. Ligands according to claim 1 , characterised in that X is nitrogen and Y represents a CR9 group.
4. Ligands according to any one of claims 1 to 3 , characterised in that the ligands carry at least one radical R1 selected from the group consisting of phenyl, Cι-Cιo-alkyl, cyclopentyl, cyclohexyl, cyclo- heptyl, 1-adamantyl, 2-adamantyl, 5H-dibenzo- phospholyl, 9-phosphabicyclo [3.3.1]nonanyl , 9-phospha- bicyclo[4.2.l]nonanyl radicals.
5. Ligands according to any one of claims 1 to 4, characterised in that the ligand radicals R2 to R9 are selected from the group hydrogen, Ci-Cio-alkyl, C2-C3.0- alkenyl, Cι-Cιo-haloalkyl, C3-C8-cycloalkyl, Ce-Cio- aryl, C2-C6-heteroaryl, wherein from 1 to 3 nitrogen atoms or an oxygen or sulfur atom may be present as hetero atom and wherein two adjacent radicals R2 to R9 may be bridged with one another.
6. Catalysts containing at least one metal of sub-group VIII and at least one phosphane ligand according to any one of the preceding claims 1 to 5.
7. Catalyst according to claim 6, characterised in that it contains at least one palladium, nickel, platinum, rhodium, iridium, ruthenium and cobalt atom or ion as transition metal .
8. Catalyst according to either claim 6 or claim 7 , characterised in that the catalyst is a mono- , di- , tri- or tetra-phosphane complex of the transition metal .
9. Use of ligands according to any one of claims 1 to 5 or of catalysts according to any one of claims 6 to 8 in the catalytic preparation of dienes or arylated olefins (Heck reactions) , biaryls (Suzuki reactions) , α-aryl ketones or amines from aryl halides or vinyl halides.
10. Use of ligands according to any one of claims 1 to 5 or of catalysts according to any one of claims 6 to 8 in the catalytic carbonylation of aryl halides, alkynylations using alkynes (Sonogashira couplings) and cross-couplings using organometallic reagents.
11. Use of ligands according to any one of claims 1 to 5 or of catalysts according to any one of claims 6 to 8 in the catalytic preparation of aryl olefins, dienes, diaryls, benzoic acid derivatives, acrylic acid derivatives, arylalkanes, alkynes or amines.
12. Process for the catalytic preparation of aryl olefins, dienes, diaryls, benzoic acid derivatives, acrylic acid derivatives, arylalkanes, alkynes, aryl ketones, carbonyl compounds or amines from aryl halides or vinyl halides, characterised in that catalysts according to claims 6 to 8 are used, wherein the catalyst is either fed in the form of a complex compound to the reaction mixture or is produced in si tu by mixing at least one ligand according to claims 1 to 5 and at least one transition metal salt or transition metal complex of a metal of sub-group VIII.
13. Process according to claim 12, characterised in that the reaction is carried out at temperatures of from 20 to 200°C.
14. Process according to either claim 12 or claim 13, characterised in that the phosphane ligand is used in excess relative to the transition metal in a ratio of transition metal to ligand of from 1:1 to 1:1000.
15. Process according to claim 14, characterised in that the ratio of transition metal to ligand is from 1:1 to
1:100.
16. Process according to any one of claims 12 to 15 the transition metal is used in a ratio of from 5 mol . % to 0.001 mol.% relative to the substrate.
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JP2007505945A (en) 2007-03-15
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US7589081B2 (en) 2009-09-15
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CN1791606A (en) 2006-06-21
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