Rhodium Containing Patents (Class 502/166)
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Patent number: 6020532Abstract: A process for preparing aldehydes by hydroformylating olefinically unsaturated compounds in the presence of a water-insoluble catalyst composition comprising rhodium complexes containing diphosphine ligands, wherein the diphosphine ligands present are compounds of the formula (I) ##STR1## wherein R.sup.1 is selected from the group consisting of carboxylate (COO.sup.-), sulfonate (SO.sub.3.sup.-), phosphonate (PO.sub.3.sup.2-) and 2-anmino ethtanebisphosphonate, R.sup.Type: GrantFiled: July 9, 1998Date of Patent: February 1, 2000Assignee: Hoechst AktiengesellschaftInventors: Helmut Bahrmann, Peter Lappe, Thomas Muller
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Patent number: 6017843Abstract: The present invention discloses an improved catalyst composition for preparing 5-formylvalerate esters by hydroformylation of pentenoic esters monoxide with good activity, high selectivity in the presence of hydrogen and carbon.Type: GrantFiled: June 19, 1998Date of Patent: January 25, 2000Assignee: Industrial Technology Research InstituteInventors: Jing-Cherng Tsai, Hsi-Hui Tai, Tsai-Tien Su, Bor-Ping Wang
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Patent number: 5981422Abstract: Stoichiometric and catalytic chemical transformations may be carried out in solution using novel fluorous multiphase systems (FMS). The term "fluorous" is defined as a carbon-fluorine bond rich organic molecule which is generated by replacing hydrogen atoms bonded to carbon atoms with fluorine. The novel complexes suitable for use as fluorous catalysts and reagents in the present invention contain sufficient number of fluorous moieties to render them preferentially soluble in the appropriate fluorous solvent without impairing the ability of the catalyst or reagent to be effective or participate in the corresponding reaction.Type: GrantFiled: August 26, 1997Date of Patent: November 9, 1999Assignee: Exxon Research and Engineering Co.Inventors: Istvan Tamas Horvath, Jozsef Rabai
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Patent number: 5935892Abstract: Supported phase catalysts in which the support phase is highly polar, most preferably ethylene glycol or glycerol, are disclosed. An organometallic compound, preferably a metal complex of chiral sulfonated 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) is dissolved in the support phase. Such supported phase catalysts are useful for asymmetric synthesis of optically active compounds, including the asymmetric hydrogenation of prochiral unsaturated carbon-hetero atom bonds, such as ketones, imines and beta-keto esters. The phenyl groups of the BINAP ligand are at least meno-sulfonated and the ligand overall is terra- to hexa-sulfonated. Ruthemium is the perferred metal.Type: GrantFiled: April 10, 1997Date of Patent: August 10, 1999Assignee: California Institute of TechnologyInventors: Mark E. Davis, Kam To Wan
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Patent number: 5929289Abstract: The present invention provides a hydroformylation process comprising: (1) forming a reaction mixture containing: (a) an olefinic compound, (b) hydrogen, (c) carbon monoxide, (d) a phosphite in which each phosphorus atom is bonded to three oxygen atoms and at least one such oxygen atom is bonded to a carbon atom of an aromatic ring that is adjacent to another carbon atom of said ring having a pendant monovalent group having a steric hindrance at least as great as the steric hindrance of the isopropyl group, (e) a catalytic amount of rhodium, and (f) a Group VIII metal (other than a rhodium) in an amount sufficient to reduce the rhodium-catalyzed decomposition of the phosphite during the hydroformylation process; and (2) maintaining the reaction mixture under conditions at which the olefinic compound reacts with the hydrogen and carbon monoxide to form an aldehyde.Type: GrantFiled: March 3, 1998Date of Patent: July 27, 1999Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Anthony George Abatjoglou, David Robert Bryant, John Michael Maher
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Patent number: 5922634Abstract: A water-soluble catalyst composition comprising rhodium complexes containing diphosphine ligands, wherein the diphosphine ligands present are compounds of the formula ##STR1## where R.sup.1 is selected from the group consisting of carboxylate (COO.sup.-), sulfonate (SO.sub.3.sup.-), phosphonate (PO.sub.3.sup.2-) and 2-amino ethanebisphosphonate ?NH--CH.sub.2 --CH(PO.sub.3.sup.2-).sub.2 !, R.sup.2 is selected from the group consisting of a straight-chain alkylene of 1 to 8 carbon atoms, an oxygen-containing alkylene of 2 to 6 carbon atoms, cycloalkylene of 3 to 10 carbon atoms and a member of the formulae II, III, IV or V ##STR2## a, b, c, d, e, f, g, h, k and l are individually 0 to 1, where at least one of a, b, c, d, e, f, g, h, k or l has to be equal to 1, x(s) are individually 0 or 1, y is an integer of 1 to 24, R.sup.3 and R.sup.Type: GrantFiled: April 17, 1997Date of Patent: July 13, 1999Assignee: Hoechst AktiengesellschaftInventors: Helmut Bahrmann, Peter Lappe, Thomas Muller
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Patent number: 5872273Abstract: A novel diphosphine compound of the formula (I): ##STR1## where R.sup.1 and R.sup.2 represent independently cycloalkyl, unsubstituted or substituted phenyl, or a five-membered heteroaromatic ring. The compound is useful as a ligand for an asymmetric reaction, in particular, as an asymmetric hydrogenation catalyst.Type: GrantFiled: December 22, 1997Date of Patent: February 16, 1999Assignee: Takasago International CorporationInventors: Takao Saito, Tohru Yokozawa, Xiaoyaong Zhang, Noburo Sayo
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Patent number: 5858905Abstract: Catalyst systems which comprise a transition metal and a pyrophosphite ligand are particularly effective as catalysts for hydrosilation reactions. The transition metal is from groups 7-11 of the Periodic Table, and the pyrophosphite has the following formula: ##STR1## wherein E and E' are independently a direct bond, --S--, --Se--, or --CR.sub.9 R.sub.10 -- where R.sub.9 and R.sub.10 are independently hydrogen or alkyl of 1-18 carbon atoms, and R.sub.10 can also be phenyl. R is H or methyl, R.sub.1-8 are independently H, C.sub.1-18 alkyl, C.sub.5-12 cycloalkyl, or C.sub.7-15 phenylalkyl.Type: GrantFiled: July 23, 1997Date of Patent: January 12, 1999Assignee: Ciba Specialty Chemicals CorporationInventors: Andrea R. Smith, Stephen D. Pastor
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Patent number: 5827794Abstract: The present invention relates to water soluble chiral sulfonated 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl and its use as organometallic catalysts for asymmetric synthesis of optically active compounds. Asymmetric reactions of the present invention include those reactions in which organometallic catalysts are commonly used. Such reactions include, but are not limited to, reduction and isomerization reactions on unsaturated substrates and carbon--carbon bond forming reactions. Examples of such reactions include, but are not limited to, hydrogenation, hydroboration, hydrosilylation, hydride reduction, hydroformylation, alkylation, allylic alkylation, arylation, alkenylation, epoxidation, hydrocyanation, disilylation, cyclization and isomerization reactions.The catalysts of the present invention provide the advantage of functioning in the presence of water without loss in enantioselectivity relative to the nonsulfonated BINAP catalyst in an organic solvent.Type: GrantFiled: September 28, 1995Date of Patent: October 27, 1998Assignee: California Institute of TechnologyInventors: Mark E. Davis, Kam To Wan
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Patent number: 5817848Abstract: The invention relates to a bidentate phosphine ligand, the phosphorus atoms of the phosphine being connected via a bridge group, the bridge group of the bidentate phosphine ligand consisting of an ortho-anellated annular system, comprising two aryl groups, which aryl groups are connected by two bridges, the first bridge consisting of an --O-- or an --S-- atom and the second bridge being a group that contains an oxygen, sulphur, nitrogen, silicon or carbon atom or a combination of these atoms, the two phosphorus atoms being connected to the two aryl groups of the bridge group at the ortho-position relative to the --O-- or --S-- atom of the first bridge.The invention also relates to the use of this bidentate phosphium ligand in a catalyst system comprising also a transition metal compound which is used in the following type of reactions: hydroformylation hydrogenation, hydrocyanation, polymerization, isomerisation, carboxylation, cross coupling and metathesis.Type: GrantFiled: November 6, 1996Date of Patent: October 6, 1998Assignee: DSM N.V.Inventors: Paulus C. J. Kamer, Mirko Kranenburg, Petrus W. N. M. van Leeuwen, Johannes G. de Vries
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Patent number: 5801261Abstract: The invention relates to enantiomerically pure bisphosphines of the general formula (I) ##STR1## where R is as defined in the description,a process for their preparation and their use in metal complexes as catalysts for asymmetric reactions, in particular asymmetric hydrogenations.Type: GrantFiled: October 17, 1997Date of Patent: September 1, 1998Assignee: Bayer AktiengesellschaftInventors: Christian Laue, Georg Schroder, Dieter Arlt
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Patent number: 5789333Abstract: The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilation, olefin oxidation, isomerization, hydrocyanation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical.Type: GrantFiled: March 5, 1997Date of Patent: August 4, 1998Assignee: Iowa State University Research Foundation, Inc.Inventors: Robert J. Angelici, Hanrong Gao
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Patent number: 5731255Abstract: A carbonylation catalytic system comprises (A) a combination of (A1) a Group VIII metal source of Periodic Table of the Elements (e.g., palladium, palladium chloride) supported on a carrier, (A2) a ligand such as triphenylphosphine and (A3) an acid such as an alkyl-sulfonic acid, or (B) a combination of (B1) the Group VIII metal source except for palladium (e.g., a platinum compound), (B2) a ligand such as triphenylphosphine and (B3) an electron donative compound having an electron donability .DELTA..nu.D of not less than 2 (for instance, an amine such as a heterocyclic tertiary amine). The catalytic system (B) may further comprise (B4) an acid such as methanesulfonic acid.Type: GrantFiled: July 20, 1995Date of Patent: March 24, 1998Assignee: Daicel Chemical Industries, Ltd.Inventors: Li Rui Pan, Tomohide Ina, Kazuyuki Matsuoka
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Patent number: 5625107Abstract: The present invention relates to a new catalyst for converting methane into ethane, preparation thereof, and process for manufacturing ethylene using said catalyst. The conversion reaction catalyst in the present invention is employed in converting directly methane or methane-containing gas in the presence of the above catalyst with the following general formula (1).Ma.Pc.D/S (1)Where,M is a metal cluster or metal complex compound selected from the group of VIII, VII and VI series;S is an inorganic carrier;P is a promoter of phosphorus compound;D is a cobalt compound.And "a" is weight percentage of metal cluster or metal complex compound in catalyst, having a value of 0.01 to 10, "c" is weight percentage of promoter in catalyst, ranging from 1.0 to 35.0.Type: GrantFiled: August 30, 1995Date of Patent: April 29, 1997Assignee: Korea Research Institute of Chemical TechnologyInventors: Dae C. Park, Pyung K. Ahn
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Patent number: 5580991Abstract: The disclosure describes a method for separating a ruthenium complex, which comprises removing an objective hydrogenation reaction product from a hydrogenation reaction solution of an organic carbonyl compound in the presence of a ruthenium complex having a tertiary organic phosphorus compound as ligand to obtain a catalyst solution, contacting said catalyst solution with a polar solvent, and carrying out a phase-separation into a liquid phase substantially composed of the polar solvent and an another liquid phase substantially containing the ruthenium complex.Type: GrantFiled: April 4, 1995Date of Patent: December 3, 1996Assignee: Mitsubishi Chemical CorporationInventors: Hitoshi Sugiyama, Kazunari Takahashi, Haruhiko Kusaka
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Patent number: 5574171Abstract: Enantioselective hydroformylation of vinyl compounds using a catalyst composition of a chiral carbohydrate phosphorous ligand with a Rh, Pt, Co or Ir metal, to produce chiral 2-substituted propanals, wherein the phosphorous of the ligand is substituted with electron withdrawing groups.Type: GrantFiled: April 24, 1995Date of Patent: November 12, 1996Assignee: E. I. Du Pont de Nemours and CompanyInventors: Timothy A. Ayers, Thaliyil V. Rajanbabu
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Patent number: 5565398Abstract: Sulfonated diphosphines of the formula ##STR1## in which Ar is m--C.sub.6 H.sub.4 --SO.sub.3 M, M is hydrogen, ammonium, a monovalent metal, or the chemical equivalent of a polyvalent metal; Ph is phenyl; the m's are individually 1 or 2, and the n's are individually 0, 1, or 2. A method of their preparation and the hydroformylation of olefins and olefinically unsaturated compounds using these compounds as a constituent of water-soluble catalyst systems are also disclosed.Type: GrantFiled: November 2, 1995Date of Patent: October 15, 1996Assignee: Hoechst AktiengesellschaftInventors: Wolfgang A. Herrmann, Rainer Manetsberger, Helmut Bahrmann, Christian Kohlpaintner
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Patent number: 5556998Abstract: The present invention provides a novel transition metal complex which catalyzes asymmetric hydrogenation reaction. The present invention also provides a process for the preparation of the foregoing novel complex. The present invention further provides an asymmetric hydrogenation catalyst comprising the foregoing novel complex.Type: GrantFiled: March 13, 1995Date of Patent: September 17, 1996Assignee: Takasago International CorporationInventors: Akira Miyashita, Takeshi Chiba, Hiroyuki Nohira, Hidemasa Takaya
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Patent number: 5516739Abstract: A catalyst and method for the co-and terpolymerization of monomers of ethylene, other olefins, and alkynes with carbon monoxide is provided. Such a catalyst a method can be used for form living polymers. The catalyst of the present invention comprises an active cationic portion of the formula ##STR1## wherein M is a Group VIII metal, L.sup.1 and L.sup.2 are two electron donor ligands or are joined to form a bidentate four electron donor ligand, R is alkyl, aryl or acyl, and L.sup.3 is CO or a ligand capable of being displaced by CO; and a non-coordinating anionic portion, soluble in inert solvents of the formulaX.sub.n G.sup.-wherein G is B, CH, N, SO.sub.3, SO.sub.3 CH, R.sub.f SO.sub.2 CH, or NSO.sub.2 R.sub.f wherein R.sub.f is C.sub.n F.sub.2+1 where n is 1 to 10 and X is F,R.sub.f SO.sub.2, FSO.sub.2 or C.sub.6 H.sub.(5-m) Z.sub.m wherein Z is F, C1, a hydrocarbyl radical, substituted hydrocarbyl radical or combinations thereof, and m is from 1 to 5, and n of X.sub.n is from 1 to 4.Type: GrantFiled: November 24, 1993Date of Patent: May 14, 1996Assignees: The University of North Carolina at Chapel Hill, The University of North Carolina at GreensboroInventors: James C. Barborak, Maurice S. Brookhart
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Patent number: 5498584Abstract: Disclosed in a process for the homogeneous, catalytic hydrogenation of epoxyalkenes and epoxycyclo-alkenes, especially conjugated .gamma.,.delta.-epoxyalkenes and epoxycycloalkenes, to the corresponding epoxyalkanes and epoxycycloalkanes using a solution of a complex rhodium catalyst whereby the olefinic unsaturation is hydrogenated without significant hydrogenolysis of the conjugated epoxy group.Type: GrantFiled: September 23, 1994Date of Patent: March 12, 1996Assignee: Eastman Chemical CompanyInventor: Thomas A. Puckette
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Patent number: 5488153Abstract: A process or the liquid phase carbonylation of methanol or a reactive derivative thereof comprises contacting carbon monoxide with a liquid reaction composition comprising methanol or a reactive derivative thereof, a halogen promoter and a rhodium catalyst system comprising a rhodium component and a bidentate phosphorus-sulphur ligand, the ligand comprising a phosphorus dative center linked to a sulphur dative or anionic center by a substantially unreactive backbone structure comprising two connecting carbon atoms or a connecting carbon and a connecting phosphorus atom. Novel rhodium ligand complexes of formula [Rh(CO)L].sub.m and Rh(CO)LY] wherein Y is a halogen, m is a number less than 10 and L is ##STR1## wherein the R groups are independently selected from C.sub.1 to C.sub.20 alkyl, cycloalkyl, aryl, substituted aryl and optionally substituted aralkyl; the R.sup.5 groups are selected from hydrogen, C.sub.1 to C.sub.Type: GrantFiled: June 21, 1994Date of Patent: January 30, 1996Assignee: BP Chemicals LimitedInventors: Michael J. Baker, Jonathan R. Dilworth, John G. Sunley, Nigel Wheatley
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Patent number: 5481006Abstract: A process and catalyst composition are provided for the highly efficient enantioselective hydrogenation of dehydroamino acid derivatives. The catalyst composition comprises rhodium or iridium and a diphosphinite carbohydrate ligand, wherein the phosphorous atoms are attached to aromatic groups substituted with electron-donating substituents. Also provided is a means to selectively produce .alpha. amino acids in either the L or the D form, based upon use of a sugar in the ligand with phosphinites attached in an absolute Right-Left or Left-Right configuration, respectively.Type: GrantFiled: January 11, 1994Date of Patent: January 2, 1996Assignee: E. I. Du Pont de Nemours and CompanyInventors: Timothy A. Ayers, Thaliyil V. Rajanbabu
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Patent number: 5449653Abstract: A process for producing a 1,3-diol, e.g., 1,3-propanediol, and/or a 3-hydroxyaldehyde, e.g., 3-hydroxypropionaldehyde, is disclosed which comprises contacting a combination of an epoxide, carbon monoxide and hydrogen in the presence of a rhodium-containing.catalyst composition effective to promote the hydroformylation of the epoxide at conditions effective to form at least one of a 1,3-diol and a 3-hydroxyaldehyde. The rhodium-containing catalyst composition comprises an anionic rhodium-containing complex. A promoter component is preferably provided to enhance at least one of the rate and selectivity of the epoxide hydroformylation reaction. Rhodium-containing compositions and a processes for producing rhodium-containing compositions are also disclosed.Type: GrantFiled: February 5, 1993Date of Patent: September 12, 1995Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: John R. Briggs, John M. Maher, Arnold M. Harrison
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Patent number: 5411995Abstract: Xanthate, dithiocarbamate and dithiophosphate salts of transition metals, together with a coinitiator selected from organic halogen and tertiary amine compounds provide light activated initiator systems for radically polymerizable ethylenically unsaturated compounds such as (meth)acrylate esters.Type: GrantFiled: April 8, 1993Date of Patent: May 2, 1995Assignee: Loctite CorporationInventor: Darchun B. Yang
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Patent number: 5391773Abstract: Disclosed is a process for the homogeneous, catalytic hydrogenation of epoxyalkenes and epoxycycloalkenes, especially conjugated .gamma.,.delta.-epoxyalkenes and .gamma.,.delta.-epoxycycloalkenes, to the corresponding epoxyalkanes and epoxycycloalkanes using a solution of a complex rhodium catalyst whereby the olefinic unsaturation is hydrogenated without significant hydrogenolysis of the conjugated epoxy group.Type: GrantFiled: June 17, 1994Date of Patent: February 21, 1995Assignee: Eastman Chemical CompanyInventor: Thomas A. Puckette
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Patent number: 5387569Abstract: A catalyst solution comprising one or more compounds of a metal catalyst and an organic solvent selected from the group consisting of a glycol derivative, an alkyl pyrrolidone, and an alkoxy ethyl ether, wherein no additional chloride-containing compounds are added to the solution. The metal can be selected from the group consisting of platinum, rhenium and rhodium. The compounds can be selected from the group consisting of H.sub.2 PtCl.sub.6.6H.sub.2 O, Re.sub.2 (CO).sub.10, Re.sub.2 O.sub.7, LiReO.sub.4 and RhCl.sub.3.4H.sub.2 O. The catalytic solutions are useful in conversion of pollutants from automotive engines and the like. In a particularly preferred embodiment, the solution contains three metals: platinum, rhenium, and rhodium.Type: GrantFiled: February 25, 1992Date of Patent: February 7, 1995Assignee: Blue Planet Technologies Co., L.P.Inventors: Eugene Shustorovich, Richard Montano, Aleksandr Bragin, Veniamin Kalner, Konstantin Solntsev, Nikolai Moiseev, Yuri Buslaev
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Patent number: 5352813Abstract: An improved process is provided for the carbonylation of methanol to acetic acid and/or its derivatives, especially methyl acetate, under mild reaction conditions using a novel catalyst precursor. The precursor is a transition metal complex having a heterodifunctional bidentate phosphorus--nitrogen ligand attached to the metal. The carbonylation reaction can now typically be carried out at 80.degree. C. and CO pressure of 40 p.s.i.g.Type: GrantFiled: September 3, 1991Date of Patent: October 4, 1994Assignee: University of AlbertaInventors: Ronald G. Cavell, Kattesh V. Katti
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Patent number: 5334791Abstract: A process is provided for hydrogenating a non-aromatic unsaturated hydrocarbon, comprising reacting the hydrocarbon with a catalyst precursor which includes a source of a group VIIIB transition metal from the second or third rows of the periodic table and a heterobifunctional ligand constructed with a phosphine center and an imine nitrogen center, in the presence of hydrogen and a promoter selected from secondary or tertiary acyclic alkyl amines in a suitable solvent which solubilizes the hydrocarbon, the catalyst precursor, the hydrogen, and the promoter.Type: GrantFiled: May 22, 1992Date of Patent: August 2, 1994Assignee: Ligands Inc.Inventors: Ronald G. Cavell, David J. Law, Robert W. Reed
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Patent number: 5321139Abstract: Two processes are described for the preparation of the optically pure compounds of formula 1: ##STR1## in which R.sup.1 and R.sup.2 are e.g. alkyl, R.sup.3 and R.sup.4 are e.g. hydrogen and R.sup.5 is e.g. hydrogen. Both processes include, as key steps, the enantioselective hydrogenation of a C.dbd.C double bond and the regioselective formation of a dicarboxylic acid monoamide derivative. In one process a phenylitaconic acid derivative is asymmetrically hydrogenated to give an optically active (R)-benzylsuccinic acid which is then converted to a diester, said diester being converted to the monoamide compound of formula 1. In the second process, a phenylitaconic acid derivative is converted to its anhydride, and the anhydride is then converted to a monoamide which is then asymmetrically hydrogenated to give the compound of formula 1.Type: GrantFiled: February 16, 1993Date of Patent: June 14, 1994Assignee: Hoechst AktiengesellschaftInventors: Ulrich Lerch, Heiner Jendralla, Bernhard Seuring, Rainer Henning
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Patent number: 5308819Abstract: Compounds where a solid carrier material which contains diphosphine rhodium or iridium complexes fixed on the surface thereof, of which the carrier material has the formula IV or IVa: ##STR1## wherein Y denotes two monoolefin ligands or a diene ligand, M is Ir(I) or Rh(i), Z is --Cl, --Br or -I, A.crclbar. is the anion of an oxyacid or complex acid, T is a solid carrier material, r is 0, 1 or 2, and R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are as defined in claim 1. These materials are heterogeneous and separable catalysts for the asymmetrical hydrogenation of prochiral compounds containing carbon double bonds or carbon/hetero atom double bonds, for example ketones and imines.Type: GrantFiled: July 14, 1993Date of Patent: May 3, 1994Assignee: Ciba-Geigy CorporationInventors: Benoit Pugin, Felix Spindler, Manfred Muller
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Patent number: 5276210Abstract: An improved allyl alcohol hydroformylation process and catalyst are disclosed. The process uses a catalyst system comprising a Group VIII metal carbonyl complex catalyst, a trisubstituted phosphine, a neutral Group VIII(a) metal complex cocatalyst, and optionally, a diphosphinoalkane. The process uniquely gives an enhanced linear:branched aldehyde product ratio.Type: GrantFiled: March 29, 1993Date of Patent: January 4, 1994Assignee: ARCO Chemical Technology, L.P.Inventors: Rangasamy Pitchai, Anne M. Gaffney, Manish K. Nandi, Yuan-Zhang Han
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Patent number: 5266545Abstract: A catalyst composition useful in the preparation of a polymer composition includes a Group VIII metal and a phosphorus bidentate ligand of the general formula (R.sub.2)(R.sub.4)P--R.sub.3 --P(R.sub.2)(R.sub.4) wherein R.sub.2 and R.sub.4 are optionally polar substituted alkyl groups, differing from each other in carbon number, and wherein R.sub.3 is a divalent organic bridging group which contains four atoms. Such catalyst compositions are particularly useful for preparing copolymers of carbon monoxide with .alpha.-olefins having at least three carbon atoms.Type: GrantFiled: January 21, 1993Date of Patent: November 30, 1993Assignee: Shell Oil CompanyInventors: Peter A. A. Klusener, Johannes J. M. Snel
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Patent number: 5260491Abstract: Cationic rhodium bis(dioxaphosphorus heterocycle) complexes of the formula: ##STR1## in which R is preferably ##STR2## or (CH.sub.2).sub.2-5, Y . . . Y is any backbone chain of 2-5 atoms, and L and L' are any stabilizing ligands, used in hydroformylation of olefins to obtain regioselectivity of branched aldehyde products. The formula of the catalyst may include substituents which do not interfere with the branched product regioselectivity of the catalyst as a whole. In the hydroformylation method the olefin is reacted with hydrogen and carbon monoxide in the presence of the catalyst at a temperature and pressure sufficient to permit the desired branched product regioselectivity.Type: GrantFiled: October 27, 1992Date of Patent: November 9, 1993Assignee: New York UniversityInventors: Donald J. Wink, Thomas J. Kwok
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Patent number: 5242878Abstract: Polyketones can be formed from carbon monoxide and at least one olefin by using, as a catalytic complex, a catalyst which comprises a Group VIII metal, an anion of an acid having a pK.sub.a of less than about four, and a tin tetradentate phosphine ligand, preferably of the formula Sn(RPR'.sub.2).sub.4 where R is methylene and R' is phenyl.Type: GrantFiled: April 8, 1992Date of Patent: September 7, 1993Assignee: Akzo N.V.Inventor: David L. Kershner
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Catalysts for producing 1,3-diols and/or 3-hydroxyaldehydes, and processes for making and using same
Patent number: 5225387Abstract: A process for producing a 1,3-diol, e.g., 1,3-propanediol, or a 3-hydroxyaldehyde is disclosed which comprises contacting a combination of an epoxide, carbon monoxide and hydrogen in the present of a rhodium-containing catalyst effective to promote the hydroformylation of the epoxide at conditions effective to form at least one of a 1,3-diol and a 3-hydroxyaldehyde, the contacting occurring in the substantial absence of a promoting amount of alkali metal ions, and at least a portion of the rhodium-containing catalyst being formed substantially without incorporation of the epoxide. A process for producing such rhodium-containing compositions is also disclosed.Type: GrantFiled: April 25, 1991Date of Patent: July 6, 1993Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: John R. Briggs, John M. Maher, Arnold M. Harrison -
Patent number: 5223648Abstract: The hydroformylation of olefins and olefinically unsaturated compounds in the presence of a water-soluble rhodium complex compound Which contains, as a ligand, at least one sulfonated diphosphine, and a catalyst therefor.Type: GrantFiled: August 25, 1992Date of Patent: June 29, 1993Assignee: Hoechst AktiengesellschaftInventors: Wolfgang Herrmann, Christian Kohlpaintner, Helmut Bahrmann
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Patent number: 5217760Abstract: Xanthate, dithiocarbamate and dithiophosphate salts of transition metals, together with a coinitiator selected from organic halogen and tertiary amine compounds provide light activated initiator systems for radically polymerizable ethylenically unsaturated compounds such as (meth)acrylate esters.Type: GrantFiled: July 20, 1990Date of Patent: June 8, 1993Assignee: Loctite CorporationInventor: Darchun B. Yang
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Patent number: 5210318Abstract: A process for producing a 1,3-diol, e.g., 1,3-propanediol, and/or a 3-hydroxyaldehyde, e.g., 3-hydroxypropionaldehyde, is disclosed which comprises contacting a combination of an epoxide, carbon monoxide and hydrogen in the presence of a rhodium-containing catalyst composition effective to promote the hydroformylation of the epoxide at conditions effective to form at least one of a 1,3-diol and a 3-hydroxyaldehyde. The rhodium-containing catalyst composition comprises an anionic rhodium-containing complex. A promoter component is preferably provided to enhance at least one of the rate and selectivity of the epoxide hydroformylation reaction Rhodium-containing compositions and a processes for producing rhodium-containing compositions are also disclosed.Type: GrantFiled: March 18, 1991Date of Patent: May 11, 1993Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: John R. Briggs, John M. Maher, Arnold M. Harrison
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Patent number: 5200380Abstract: The hydroformylation of olefins and olefinically unsaturated compounds in the presence of a water-soluble rhodium complex compound which contains, as a ligand, at least one sulfonated diphosphine, and a catalyst therefor.Type: GrantFiled: December 6, 1991Date of Patent: April 6, 1993Assignee: Hoechst AktiengesellschaftInventors: Wolfgang Herrmann, Christian Kohlpaintner, Helmut Bahrmann
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Patent number: 5187134Abstract: This invention relates to formed, polymeric complexes of metals of the eighth subgroup of the periodic system with ligands of an organosiloxane copolycondensate optionally cross-linked by means of cross-linking agents containing Si, Ti, Zr and/or Al, in the form of statistical, block or mixed copolycondensates. The ratio between the number of moles of phosphine units and the number of moles of bound metal atoms is 1:1 to 1000 to 1 and the ratio between the amine units and the phosphine is preferably 5:95 to 95:5 mole %. The polymeric complex compounds are present macroscopically as spherical particles with a diameter in the range of 0.01 to 3.0 mm, a BET surface of greater than 0 to 1000 m.sup.2 /g, a specific pore volume of 0.01 to 6.5 ml/g and a bulk density of 50 to 1000 g/l. The invention also includes several methods of preparing the complexes with post-treatment stages and the use of the polymeric metal complexes as catalysts in organic chemistry.Type: GrantFiled: November 1, 1991Date of Patent: February 16, 1993Assignee: Degussa AGInventors: Peter Panster, Robert Gradl
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Patent number: 5179055Abstract: Cationic rhodium bis(dioxaphosphorus heterocycle) complexes of the formula: ##STR1## in which R is preferably ##STR2## or (CH.sub.2).sub.2-5, Y . . . Y is any backbone chain of 2-5 atoms, and L and L' are any stabilizing ligands, used in hydroformylation of olefins to obtain regioselectivity of branched aldehyde products. The formula of the catalyst may include substituents which do not interfere with the branched product regioselectivity of the catalyst as a whole. In the hydroformylation method the olefin is reacted with hydrogen and carbon monoxide in the presence of the catalyst at a temperature and pressure sufficient to permit the desired branched product regioselectivity.Type: GrantFiled: September 24, 1990Date of Patent: January 12, 1993Assignee: New York UniversityInventors: Donald J. Wink, Thomas J. Kwok
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Patent number: 5177044Abstract: A novel catalyst composition containing a Group VIII metal and a phosphorus bidentate ligand wherein each phosphorus atom forms part of a phosphacyclohexyl structure.Type: GrantFiled: November 20, 1991Date of Patent: January 5, 1993Assignee: Shell Oil CompanyInventors: Johannes A. van Doorn, Johannes J. M. Snel, Peter A. A. Klusener
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Patent number: 5175311Abstract: A chiral catalyst is disclosed together with methods of using it for enantioselective syntheses. The chiral catalyst includes a nucleus with two metal atoms that has four bridging ligands oriented radially to the axis of the nucleus. Each of these ligands includes two complexing atoms each complexed to one of the metal atoms. At least one of the bridging ligands includes a chiral center which is bonded to one of the complexing atoms. Preferably, all four of the bridging ligands include a chiral center bonded to one of the complexing atoms. The catalyst of the invention has been found to be useful in catalyzing carbenoid transformation reactions such as cyclopropanation.Type: GrantFiled: March 29, 1990Date of Patent: December 29, 1992Assignee: Research Corporation Technologies, Inc.Inventor: Michael F. Doyle
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Patent number: 5162279Abstract: An immobilized metal complex is disclosed, which is immobilized on an inorganic carrier to which a long molecular chain compound capable of surrounding the metal complex is bound in an amount of at least 1.5 mols per mol of the metal complex. This novel immobilized metal complex has an excellent stability and can be used as a metal complex catalyst providing excellent reactivity.Type: GrantFiled: July 8, 1991Date of Patent: November 10, 1992Assignee: Director-General of Agency of Industrial Science and TechnologyInventor: Keiji Miki
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Patent number: 5135901Abstract: A catalyst used in a process for producing a .beta.-hydroxyester product or a .beta.-hydroxyaldehyde product from ethylene oxide, carbon monoxide, and, optionally, hydrogen, is disclosed. This process uses, as a catalyst, a catalyst comprising rhodium, ruthenium, and a Group Va promoter.Type: GrantFiled: June 7, 1991Date of Patent: August 4, 1992Assignee: Eastman Chemical CompanyInventor: William A. Beavers
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Patent number: 5124300Abstract: A catalyst system, which comprises:a) a source of a Group VIII metal;b) a phosphine having an aromatic substituent which contains an imino nitrogen atom;c) a source of protons; andd) a tertiary amine.Type: GrantFiled: February 4, 1991Date of Patent: June 23, 1992Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 5124294Abstract: The present invention concerns a catalyst system and a process for selectively producing alcohols from olefines and synthesis gas. The catalyst system comprises one or several metal cluster compounds belonging to the cobalt group on an inorganic carrier and an amine of the form NR.sub.1 R.sub.2 R.sub.3, where R.sub.1,R.sub.2 and R.sub.3 are either hydrogen or an aliphatic or aromatic group containing 1 to 8 carbon atoms.Type: GrantFiled: August 25, 1987Date of Patent: June 23, 1992Assignee: Neste OyInventors: Leila Alvila, Tapani Pakkanen, Outi Krause, Matteus Joutsimo
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Patent number: 5113022Abstract: This invention relates to novel ionic phosphites and the use thereof as ligands in homogenous transition metal catalyzed processes, especially hydroformylation.Type: GrantFiled: August 8, 1991Date of Patent: May 12, 1992Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Anthony G. Abatjoglou, David R. Bryant
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Patent number: 5086027Abstract: A catalyst composition comprised of: about 0.005 to 5.0 wt. % noble metal, about 0.5 to 5 wt. % of at least one Group VIII metal, and about 3 to 18 wt. % of a Group VI metal, and a refractory support, wherein the noble metal is incorporated into the refractory support by use of a precursor represented by ML.sub.2 when the noble metal is Pt or Pd and ML.sub.3, when the noble metal is Rh or Ir, where M is the noble metal and L is a ligand selected from the dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, and further wherein L has organo groups having a sufficient number of carbon atoms to render the noble metal complex soluble in oil.Type: GrantFiled: December 18, 1990Date of Patent: February 4, 1992Assignee: Exxon Research and Engineering CompanyInventors: Gopal H. Singhal, William E. Winter, Kenneth L. Riley, Kenneth L. Trachte
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Patent number: 5075470Abstract: A process for the preparation of .mu.-3-carbopentazane-N.sup.1, N.sup.4 :N.sup.2, N.sup.5 -bis-[bis(triphenylphosphine)rhodium (I)] dinitrate by the reaction of tris(triphenylphosphine)nitratorhodium (I) with hydrazine in degassed methanol under an inert atmosphere.Type: GrantFiled: July 26, 1990Date of Patent: December 24, 1991Assignee: Plurichemie AnstaltInventors: William Heggie, Philip R. Page, Ivan Villax, Indira Ghatak, Michael B. Hursthouse