Forming Amine Group Directly By Reduction Patents (Class 564/415)
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Publication number: 20020016513Abstract: The first embodiment of the present invention provides a process, which includes:Type: ApplicationFiled: January 24, 2001Publication date: February 7, 2002Applicant: Degussa-Huels AktiengesellschaftInventors: Stephan Laue, Andreas Liese, Christian Wandrey, Olaf Burkhardt, Jens Woeltinger, Andreas Bommarius, Karlheinz Drauz, Jean-Louis Philippe, Hans Henniges, Adreas Karau
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Publication number: 20020010369Abstract: Residues from the distillation of a toluene diamine phosgenation mixture are hydrolyzed by mixing them with water and subjecting the mixture to a temperature of 200-350° C. The hydrolysis is performed in the presence of a sufficient amount of a base to maintain the pressure in the reactor to no more than a predetermined operating level. The product mixture is then extracted to recover TDA, which can be recycled. This provides an efficient process whereby nearly quantitative conversion of the residues to TDA can be achieved.Type: ApplicationFiled: May 5, 2000Publication date: January 24, 2002Inventors: Shenghong Dai, Duane S. Treybig, Kathryn Hock, Van A. Kent
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Patent number: 6284925Abstract: The use of the ligands and complexes of general formula I and II for catalytic, enantioselective hydrogenation.Type: GrantFiled: June 18, 1999Date of Patent: September 4, 2001Assignee: Degussa-Huls AGInventors: Paul Knochel, Juan Jose Almena Perea, Karlheinz Drauz, Ingo Klement
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Publication number: 20010004672Abstract: A process for the modification of a hydrogenation catalyst of the Raney nickel, Raney cobalt, nickel-on-carrier or cobalt-on-carrier type, which process includes treating the hydrogenation catalyst at temperatures of about 0° C. to about 120° C. with carbon monoxide, carbon dioxide, formaldehyde, a lower aliphatic aldehyde, an aromatic aldehyde, an aliphatic ketone, an aromatic ketone, a mixed aliphatic/aromatic ketone, glyoxal, pyruvaldehyde or glyoxylic acid as the modification agent in a liquid dispersion medium consisting of water or an organic solvent for a duration of about 15 minutes to about 24 hours. When the thus-modified catalyst is used in the hydrogenation of a nitrile to the corresponding amine, the selectivity is increased, and significantly favors the amount of the primary amine vis-à-vis the undesired secondary amine in the hydrogenation product as compared to when the corresponding unmodified catalyst is employed.Type: ApplicationFiled: November 30, 2000Publication date: June 21, 2001Inventors: Oliver Gerald Degischer, Felix Roessler
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Patent number: 6248925Abstract: This invention pertains to an improvement in a process for the formation of secondary or tertiary amines by the catalytic reductive amination of a nitrile with a primary or secondary amine and, particularly to the reductive amination of C8-20 nitrites with a secondary amine. The catalyst employed in the improved reductive amination process is one which has been promoted with a lithium salt or base, e.g., lithium chloride or lithium hydroxide.Type: GrantFiled: October 22, 1999Date of Patent: June 19, 2001Assignee: Air Products and Chemicals, Inc.Inventors: Michael Edward Ford, John Nelson Armor
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Patent number: 6222074Abstract: The invention relates to a process for preparation of 4,6-diaminoresorcinol or salts thereof by reducing 4,6-bis(substituted)phenylazoresorcinol expressed by the formula [1] wherein, R denotes a halogen atom, an alkyl group having 1-5 carbon atoms, a hydroxycarbonyl group or an alkoxy group having 1-5 carbon atoms, n denotes 0 or any integer of 1-5, and two or more groups R may be same or different each other, for example, 4,6-bisphenylazoresorcinol, with hydrogen in the presence of a metal catalyst to obtain 4,6-diaminoresorcinol or salts thereof, characterized in that an aliphatic nitrile compound (for example, acetonitrile) is used as a solvent, or characterized in that the reduction is carried out by using at least one organic solvent selected from aliphatic nitrile compounds, aliphatic alcohols having 3-5 carbon atoms, dioxane and ethylene glycol monomethyl ether, etc. as a solvent and furthermore in the presence of a filter aid (for example, active carbon).Type: GrantFiled: July 25, 2000Date of Patent: April 24, 2001Assignee: Nissan Chemical Industries, Ltd.Inventors: Kenichi Tokunaga, Motohito Shiratori, Kazuhiko Akimoto, Hideo Suzuki, Isao Hashiba
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Patent number: 6153784Abstract: Halides are removed from halide-containing nitrile mixtures by(a) thermally treating the halide-containing nitrile mixture,(b) subsequently adding a base to the thermally treated nitrile mixture and(c) subsequently separating off the base from the nitrile mixture.Amines are prepared by(A) reacting alkyl halides with metal cyanides in an at least two-phase reaction medium in the presence of halide-containing phase-transfer catalysts to give alkanenitriles,(B) separating off the resulting halide-containing alkanenitrile mixture phase and(C) further treating the halide-containing alkanenitrile mixture phase, as described in the stages(a)-(c) removing halides from halide-containing nitrile mixtures and(d) hydrogenating nitrites obtained in stage (c) to give amines, in the presence of suspended or fixed-bed catalysts.Type: GrantFiled: February 17, 1998Date of Patent: November 28, 2000Assignee: BASF AktiengesellschaftInventors: Heinz-Josef Kneuper, Hans-Jurgen Weyer, Horst Neuhauser, Johann-Peter Melder, Andreas Henne, Karl-Heinz Ross, Rainer Becker
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Patent number: 6137011Abstract: Bistrifluoromethylbenzylamines are obtained in a simple manner in high purities and with good yields by catalytic hydrogenation of the corresponding bistrifluoromethylbenzonitriles if the process is carried out in the presence of Raney cobalt, at least one aliphatic ether and ammonia.Type: GrantFiled: February 25, 2000Date of Patent: October 24, 2000Assignee: Bayer AktiengesellschaftInventors: Albrecht Marhold, Ernst Kysela
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Patent number: 6124504Abstract: The application describes a process for preparing 4-hydroxyanilines by the reaction of phenols with diazonium salts and subsequent reduction.Type: GrantFiled: June 27, 1997Date of Patent: September 26, 2000Assignee: Bayer AktiengesellschaftInventors: Achim Hupperts, Karl Steinbeck, Uwe Stelzer, Reinhard Lantzsch, Hermann Seifert
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Patent number: 6054617Abstract: The invention concerns a process for the reduction of nitro groups to amino groups, characterized that a nitro compound is reacted with hydrogen in the presence of an aqueous solution of a water-soluble metal catalyst of the formula M (L).sub.n (Y).sub.m wherein M is ruthenium, rhodium, nickel, or palladium; L, is a water soluble ligand; Y is a further ligand or an alkaline earth ion; n is 1, 2, 3, or 4; and m is 0, 1, or 2.Type: GrantFiled: May 22, 1998Date of Patent: April 25, 2000Assignee: Clariant GmbHInventors: Helmut Bahrmann, Boy Cornils, Andreas Dierdorf, Steffen Haber
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Patent number: 5994584Abstract: 4-Aminodiphenylamines are prepared by hydrogenating nitrosobenzene or mixtures of nitrosobenzene and nitrobenzene with hydrogen in the presence of fluorides and heterogeneous catalysts in inert aprotic solvents at temperatures from 0 to 200.degree. C. and pressures from 0.1 to 150 bar.Type: GrantFiled: March 8, 1999Date of Patent: November 30, 1999Assignee: Bayer AktiengesellschaftInventors: Pieter Ooms, Henrey Giera
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Patent number: 5986139Abstract: A process for the preparation of primary or secondary amines by hydrogenation of imines with hydrogen at elevated pressure and in the presence of a dinuclear Ir(III) complex having ditertiary diphosphine ligands, halide bridges, halide and hydride ligands, or an Ir(III) halide complex salt containing ditertiary diphosphine ligands, as catalyst, wherein the catalyst corresponds to formula I or Ia or to mixtures of at least two compounds of formula I, at least two compounds of formulae I and Ia, or at least two compounds of formula Ia[(DIP)IrX.sub.q Y.sub.r ].sub.2 (I),[(DIP)X.sub.4 ].sup..crclbar. Me.sup..sym. (Ia),whereinDIP is the ditertiary diphosphine ligand of a ferrocenyldiphosphine the phosphine groups of which are either bonded directly or via a bridge group --CR.sub.v R.sub.w -- to the ortho positions of a cyclopentadienyl ring or are each bonded to a cyclopentadienyl ring of a ferrocenyl, so that a 5-, 6- or 7-membered ring is formed together with the Ir atom;R.sub.v and R.sub.Type: GrantFiled: January 26, 1998Date of Patent: November 16, 1999Assignee: Novartis Crop Protection, Inc.Inventors: Rafael Sablong, John Anthony Osborn, Felix Spindler
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Patent number: 5962740Abstract: A process for producing 4,6-bisphenylazoresorcinol of formula ?2! wherein R represents halogen atom, C.sub.1-5 alkyl group, hydroxycarbonyl or C.sub.1-5 alkoxy group, n represents 0 or an integer of 1 to 5, and two or more Rs are the same or different from each other, which comprises reacting resorcinol with a benzenediazonium salt of formula ?1! wherein R and n are the same as defined in the above formula ?1!, and X represents Cl, Br, OSO.sub.3 H or OPO.sub.3 H.sub.Type: GrantFiled: April 28, 1998Date of Patent: October 5, 1999Assignee: Nissan Chemical Industries, Ltd.Inventors: Kazuhiko Akimoto, Kenichi Tokunaga, Isao Hashiba, Hideo Suzuki, Yasuo Katsumura, Kazuo Osaki, Hideo Kawashita, Satoshi Yamazaki
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Patent number: 5932768Abstract: 4-aminodiphenylamines are prepared by hydrogenating nitrosobenzene or mixtures of nitrosobenzene and nitrobenzene with hydrogen in the presence of bases containing hydroxide, oxide and/or alkoxide groups and heterogeneous catalysts in inert aprotic solvents at temperatures of from 0 to 200.degree. C. and at pressures of from 0.1 to 150 bar.Type: GrantFiled: July 30, 1998Date of Patent: August 3, 1999Assignee: Bayer AGInventors: Pieter Ooms, Ulrich Notheis, Christian Laue
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Patent number: 5925790Abstract: A method for producing aromatic amines such as N-phenyl-p-phenylenediamine is disclosed wherein an amine substituted aromatic such as aniline is oxidized with oxygen or hydrogen peroxide in the presence of a preferred trisodium pentacyano ferrate(II) complex containing various water soluble ligands, such as ammonia, mono alkyl amine, dialkyl amines, and trialkyl amines. The complex is subsequently catalytically reduced by hydrogenation using certain heterogeneous metal catalysts to yield the desired aromatic amine.Type: GrantFiled: March 13, 1997Date of Patent: July 20, 1999Assignee: Uniroyal Chemical Company, Inc.Inventors: Edward L. Wheeler, Russell E. Malz, Jr., Mark W. Simon
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Patent number: 5925791Abstract: 4-aminodiphenylamines are produced by hydrogenating nitrobenzene with hydrogen in the presence of bases containing hydroxide and/or oxide groups and heterogeneous catalysts and in the presence of inert aprotic solvents at temperatures of 0 to 200.degree. C. and pressures of 0.1 to 150 bars.Type: GrantFiled: February 27, 1998Date of Patent: July 20, 1999Assignee: Bayer AGInventors: Hans-Josef Buysch, Christian Laue, Heinrich Konigshofen, Ulrich Notheis, Pieter Ooms, Ursula Pentling
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Patent number: 5919961Abstract: Chiral compounds of the formula I ##STR1## where the variables are as described in the specification.Type: GrantFiled: May 30, 1997Date of Patent: July 6, 1999Assignee: BASF AktiengesellschaftInventors: Rainer Sturmer, Jun Okuda, Kurt Ritter
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Patent number: 5886225Abstract: A process for the hydrogenation of imines with hydrogen under elevated pressure in the presence of iridium catalysts and with or without an inert solvent, wherein the reaction mixture contains hydrogen iodide.Type: GrantFiled: December 5, 1997Date of Patent: March 23, 1999Assignee: Novartis Crop ProtectionInventors: Hans-Peter Jalett, Felix Spindler, Reinhard Georg Hanreich
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Patent number: 5874625Abstract: An improved, optimized industrial process has been found for the hydrogenation of organic nitrites into primary amines, which essentially consists of contacting a dried charge of at least one organic nitrile, aqueous alkali metal hydroxide, at least one Raney slurry hydrogenation catalyst, water and hydrogen for an effective time and at an effective temperature and pressure, wherein the improvements comprise eliminating the steps of drying the charge and adding water and reducing the required water to about 0.2%. Secondary and tertiary amine formation is low, as is moisture content and neither precious metals such as rhodium, nor strategic metals, such as cobalt nor ammonia gas nor solvents are required. Surprisingly, it has been found that water levels less than that taught in the prior art are effective at suppressing secondary and tertiary amine production, while still producing repeatable product on an industrial scale and with reduced cycle time, energy and catalyst charge.Type: GrantFiled: November 4, 1996Date of Patent: February 23, 1999Assignee: Henkel CorporationInventor: A. Fred Elsasser
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Patent number: 5869653Abstract: An improved process for the catalytic hydrogenation of nitriles. The basic process comprises contacting the nitrile with hydrogen in the presence of a sponge or Raney cobalt catalyst under conditions for effecting conversion of the nitrile group to the primary amine. The improvement in the hydrogenation process resides in effecting the hydrogenation in the presence of a catalytic amount of lithium hydroxide and water. To achieve a catalytic amount of lithium hydroxide, the catalyst may be pretreated with the lithium hydroxide and/or the reaction may be carried out with the lithium hydroxide present in the reaction medium.Type: GrantFiled: October 30, 1997Date of Patent: February 9, 1999Assignee: Air Products and Chemicals, Inc.Inventor: Thomas Albert Johnson
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Patent number: 5861535Abstract: Tertiary aminoaryl compounds, such as N,N'dialkylaminoaryl compounds, are prepared using successive reductive steps without isolation therebetween, at high temperature and pressure. A nitroaryl compound is reduced using a ketone as both solvent and reactant in a reductive environment, and the resulting intermediate is further reacted with an aldehyde in the same reaction mixture without isolation to provide the second substituent on the amino group.Type: GrantFiled: September 23, 1997Date of Patent: January 19, 1999Assignee: Eastman Kodak CompanyInventor: Victor L. Mylroie
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Patent number: 5859300Abstract: A process for the hydrogenation of imines with hydrogen under elevated pressure in the presence of iridium catalysts containing diphosphine ligands, with or without an inert solvent, the reaction mixture containing a soluble ammonium chloride, bromide or iodide or a soluble metal chloride, bromide, or iodide, wherein the reaction mixture additionally contains at least one solid acid with the exception of ion exchangers. Improved optical yields and high chemical conversion rates are achieved while the catalyst is easily separable.Type: GrantFiled: January 26, 1998Date of Patent: January 12, 1999Assignee: Novartis CorporationInventors: Hans-Peter Jalett, Bernd Siebenhaar
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Patent number: 5859299Abstract: A process is provided for the production of nitrobenzamides or aminobenzamides having the formula: ##STR1## in which n is 1 or 2, preferably 1, X is an amino or nitro group and R is hydrogen, unsubstituted alkyl or alkyl substituted by halogen, C.sub.1 -C.sub.4 -alkoxy, phenyl, carboxyl, C.sub.1 -C.sub.4 -alkoxycarbonyl, a mono- or di-C.sub.1 -C.sub.4 alkylated amino group or by --SO.sub.3 M in which M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine, which process comprises reacting a nitrobenzoyl chloride having the formula: ##STR2## in which n has its previous significance, with an aqueous solution of an amine having the formula NH.sub.2 --R in which R has its previous significance, in the presence of an inert organic solvent, to produce a compound having the formula: ##STR3## in which n and R have their previous significance; and finally optionally reducing the nitro group(s) to amino group(s).Type: GrantFiled: August 15, 1997Date of Patent: January 12, 1999Assignee: Ciba Specialty Chemicals CorporationInventor: Dieter Meier
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Patent number: 5840981Abstract: A process for preparing N-methyl-2-(3,4-dimethoxyphenyl)-ethylamine comprises hydrogenating 3,4-dimethoxyphenylacetonitrile with a methylamine of the general formula I ##STR1## where R.sup.1 is hydrogen, benzyl or tert-butyl, and hydrogen in the presence of a supported catalyst which comprises from 0.05 to 50% by weight of copper chromite, copper, silver, gold, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum or mixtures thereof, in the presence or absence of water at from 20.degree. to 200.degree. C. under from 1 to 300 bar.Type: GrantFiled: October 28, 1997Date of Patent: November 24, 1998Assignee: BASF AktiengesellschaftInventors: Eberhard Fuchs, Horst Zimmermann, Tom Witzel, Boris Breitscheidel, Rainer Becker, Horst Nauhauser
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Patent number: 5801280Abstract: A process for preparing an optically active alcohol by reacting a prochiral ketone corresponding to the optically active alcohol and an acid with a mixture of (1) a boron-containing compound selected from the group consisting of i) a borane compound which is obtained from an optically active .beta.-aminoalcohol and a boron hydride; or obtained from the optically active .beta.-aminoalcohol, a metal borohydride and an acid and ii) an optically active oxazaborolidine and (2) a metal borohydride; and a process for preparing an optically active amine by reacting an oxime derivative and an acid with a mixture of (1) a boron-containing compound selected from the group consisting of i) a borane compound which is obtained from an optically active .beta.-aminoalcohol and a boron hydride, or obtained from said optically active .beta.-aminoalcohol, a metal borohydride and an acid and ii) an optically active oxazaborolidine, and (2) a metal borohydride.Type: GrantFiled: April 5, 1996Date of Patent: September 1, 1998Assignee: Sumitomo Chemical Company, LimitedInventors: Yukio Yoneyoshi, Naoto Konya, Gohfu Suzukamo, Masashi Kamitamari, Takashi Miyawaki
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Patent number: 5750788Abstract: A process is disclosed for preparing amines by hydrogenating compounds with at least 3 cyano groups prepared by adding acrylonitrile to ammonia or primary amines at temperatures from 80.degree. to 200.degree. C. and pressures from 5 to 500 bars.Type: GrantFiled: May 19, 1997Date of Patent: May 12, 1998Assignee: BASF AktiengesellschaftInventors: Lukas Haussling, Horst Neuhauser, Wolfgang Paulus
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Patent number: 5739402Abstract: Preparation of mixtures of O-phenoxyalkylhydroxylamines Ia and Ib ##STR1## and the corresponding salt mixtures by a) converting mixtures of isomers of O-(2-hydroxyethyl)oximes IIa and IIb ##STR2## with a sulfonyl halide III ##STR3## into a mixture of sulfonates IVa and IVb ##STR4## b) reacting this mixture of IVa and IVb with a phenol HO-Ar (V) to give a mixture of O-phenoxyalkoximes VIa and VIb ##STR5## c) hydrolyzing this mixture in the presence of an acid and, if desired d) liberating the O-phenoxyalkylhydroxylamines Ia and Ib from the resulting salts using a mineral acid.Compounds Ia/Ib and VIa/VIb are important intermediates for crop protection agents.Type: GrantFiled: November 4, 1996Date of Patent: April 14, 1998Assignee: BASF AktiengesellschaftInventors: Harald Rang, Norbert Gotz, Albrecht Harreus, Dirk Borchers, Horst Hartmann, Volker Maywald, Frank Heimann, Thomas Buschulte
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Patent number: 5728882Abstract: A method for producing aromatic amines such as N-phenyl-p-phenylenediamine is disclosed wherein an amine substituted aromatic such as aniline is oxidized with oxygen or hydrogen peroxide in the presence of trisodium pentacyano ferrate(II) complexes containing various water soluble ligands, such as ammonia, mono alkyl amine, dialkyl amines, and trialkyl amines. The complex is subsequently catalytically reduced by hydrogenation using certain heterogeneous metal catalysts to yield the desired aromatic amine.Type: GrantFiled: April 4, 1996Date of Patent: March 17, 1998Assignee: Uniroyal Chemical Company, Inc.Inventors: Edward Lockwood Wheeler, Russell Edward Malz, Jr.
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Patent number: 5686616Abstract: A novel process for preparing an optically active amine by asymmetric hydrogenation of an imine compound, such as an imine compound prepared by condensing benzylamine and acetophenone, in the presence of a catalytic amount of an iridium-optically active phosphine complex and benzylamine or a benzylamine derivative. The present invention provides an optically active amine of high optical purity.Type: GrantFiled: March 14, 1996Date of Patent: November 11, 1997Assignee: Takasago International CorporationInventors: Kazuhide Tani, Tsuneaki Yamagata, Yasutaka Kataoka, Hidenori Kumobayashi
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Patent number: 5633407Abstract: A process for preparing substituted aromatic azo compounds is provided which comprises contacting a nucleophilic compound and an azo containing compound in the presence of a suitable solvent system, and reacting the nucleophilic compound and the azo containing compound in the presence of a suitable base and a controlled amount of protic material at a temperature of about 10.degree. C. to about 150.degree. C. in a confined reaction zone wherein the molar ratio of protic material to base is 0:1 to about 5:1. In another embodiment, the substituted aromatic azo compounds are further reacted with a nucleophilic compound in the presence of a suitable solvent system, a suitable base and a controlled amount of protic material at a temperature of about 70.degree. C. to about 200.degree. C. in a confined reaction zone wherein the molar ratio of protic material to base is 0:1 to about 5:1 to produce a substituted aromatic amine.Type: GrantFiled: May 18, 1995Date of Patent: May 27, 1997Assignee: Flexsys America L. P.Inventors: Michael K. Stern, Brian K-M Cheng
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Patent number: 5629449Abstract: Disclosed is a method of making 3,5-diaminobenzotrifluoride from 4-chloro-3,5-dinitrobenzotrifluoride. A solution of 4-chloro-3,5-dinitrobenzotrifluoride in an alcohol is prepared. Separately, a slurry is prepared of a palladium catalyst on a suitable substrate, at least one equivalent of magnesium oxide per equivalent of 4-chloro-3,5-dinitrobenzotrifluoride, sufficient hydrogen-donating reducing agent to reduce the 4-chloro-3,5-dinitrobenzotrifluoride to 3,5-diaminobenzotrifluoride, and an amount of alcohol sufficient to make the slurry stirrable. The solution is added to the slurry with stirring at a rate that does not exceed the reaction rate of the 4-chloro-3,5-dinitrobenzotrifluoride so that no unreacted 4-chloro-3,5-dinitrobenzotrifluoride accumulates in the slurry. The reaction mixture is heated at about 75.degree. to about 100.degree. C.Type: GrantFiled: August 17, 1992Date of Patent: May 13, 1997Assignee: Occidental Chemical CorporationInventor: David E. Albright, Jr.
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Patent number: 5627293Abstract: The invention relates to ferrocenyldiphosphine ligands containing a silylene group, ferrocenyldiphosphines bound to inorganic or polymeric organic supports by this silylene group, their preparation and also their metal complexes with transition metals such as rhodium or iridium. The invention also relates to the use of these complexes for hydrogenating organic double or triple bonds, in particular olefinic double bonds and carbon-heteroatom double bonds. The complexes are particularly suitable for enantioselective hydrogenation using chiral diphosphines and prochiral unsaturated compounds.The preparation of these immobilized ferrocenyldiphosphines has only been made possible by the provision of correspondingly functionalized ferrocenyldiphosphines. These compounds and their preparation are likewise novel.Accordingly, the invention also provides compounds of the formula I ##STR1## in which R.sub.1 is C.sub.1 -C.sub.8 alkyl, phenyl or phenyl substituted by from 1 to 3 C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.Type: GrantFiled: February 23, 1996Date of Patent: May 6, 1997Assignee: Ciba-Geigy CorporationInventor: Benoit Pugin
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Patent number: 5618980Abstract: Disclosed are (1) a method for preparing an aromatic secondary amino compound which comprises reacting an N-cyclohexylideneamino compound in the presence of a hydrogen moving catalyst and a hydrogen acceptor by the use of a sulfur-free polar solvent and/or a cocatalyst, and(2) a method for preparing an aromatic secondary amino compound which comprises reacting cyclohexanone or a nucleus-substituted cyclohexanone, an amine and a nitro compound corresponding to the amine in a sulfur-free polar solvent in the presence of a hydrogen moving catalyst, a cocatalyst being added or not added. In a further aspect, a method is provided for the preparation of aminodiphenylamine by reacting phenylenediamine and cyclohexanone in the presence of a hydrogen transfer catalyst in a sulfur-free polar solvent while using nitroaniline as a hydrogen acceptor.Type: GrantFiled: April 30, 1996Date of Patent: April 8, 1997Assignee: Mitsui Toatsu Chemicals, Inc.Inventors: Teruyuki Nagata, Chiyuki Kusuda, Masaru Wada, Kenichi Satou, Masae Uchida
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Patent number: 5618979Abstract: A process for preparing substituted aromatic amines which comprises contacting a nucleophilic compound and a substituted aromatic azo compound in the presence of a suitable solvent system, and reacting the nucleophilic compound and the substituted aromatic azo compound in the presence of a suitable base and a controlled amount of protic material at a temperature of about 70.degree. C. to about 200.degree. C. in a confined reaction zone wherein the molar ratio of protic material to base is 0:1 to about 5:1. In another embodiment, the substituted aromatic amines of the invention are reductively alkylated to produce alkylated diamines or substituted derivatives thereof.Type: GrantFiled: May 18, 1995Date of Patent: April 8, 1997Assignee: Flexsys America L. P.Inventors: Michael K. Stern, Brian K-M Cheng
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Patent number: 5608112Abstract: Nitrogen-containing substituents of aliphatic or aromatic compounds can be reduced by treatment with a reagent comprising (i) at least one complex of a transition metal of group 4 or 5 with a multidentate or unidentate organic or inorganic ligand and (ii) a reducing agent. The reaction is conducted optionally in the presence of an aliphatic or aromatic amine, and/or in the presence of an inert organic solvent.Type: GrantFiled: July 10, 1995Date of Patent: March 4, 1997Assignee: The Trustees of Princeton UniversityInventor: Jeffrey Schwartz
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Patent number: 5574189Abstract: This invention relates to an improvement in a process for the production of amines and particularly secondary amines by the hydrogenation of aliphatic and aromatic nitriles. The improvement resides in the use of a multi-metallic catalyst, preferably a bimetallic catalyst comprising nickel or cobalt in combination with rhodium, ruthenium or palladium. Optionally, the catalyst is carried on an alumina support.Type: GrantFiled: February 2, 1995Date of Patent: November 12, 1996Assignee: Air Products and Chemicals, Inc.Inventors: Gamini A. Vedage, John N. Armor
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Patent number: 5574186Abstract: There is disclosed a novel process for the enantioselective synthesis of chiral amino alcohols from keto oxime ethers, which are derived from cyclic ketones, via catalytic asymmetric reduction, employing oxazaborolidine-borane complex (OAB-BH.sub.3). In this catalytic reduction process two chiral centers are created in a single step with high levels of stereoselectivity.Type: GrantFiled: March 8, 1995Date of Patent: November 12, 1996Assignee: Merck & Co., Inc.Inventors: Charles Boudreau, Richard D. Tillyer, David M. Tschaen
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Patent number: 5536878Abstract: Disclosed are (1) a method for preparing an aromatic secondary amino compound which comprises reacting an N-cyclohexylideneamino compound in the presence of a hydrogen moving catalyst and a hydrogen acceptor by the use of a sulfur-free polar solvent and/or a cocatalyst, and (2) a method for preparing an aromatic secondary amino compound which comprises reacting cyclohexanone or a nucleus-substituted cyclohexanone, an amine and a nitro compound corresponding to the amine in a sulfur-free polar solvent in the presence of a hydrogen moving catalyst, a cocatalyst being added or not added. In a further aspect, a method is provided for the preparation of aminodiphenylamine by reacting phenylenediamine and cyclohexanone in the presence of a hydrogen transfer catalyst in a sulfur-free polar solvent while using nitroaniline as a hydrogen acceptor.Type: GrantFiled: December 2, 1994Date of Patent: July 16, 1996Assignee: Mitsui Toatsu Chemicals, Inc.Inventors: Teruyuki Nagata, Chiyuki Kusuda, Masaru Wada, Kenichi Satou, Masae Uchida
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Patent number: 5504253Abstract: A method of making (R)-N- 1-(3-methoxyphenyl)ethyl!-3-(2-chlorobenzene)propanamine which involves reducing the appropriate amidyl or iminyl precursor with an appropriate reducing agent. The appropriate amidyl or iminyl precursor is made from a synthesis involving the use of (R)-3-methoxy-.alpha.-methylbenzylamine. A method of condensing a nitrile with a primary or secondary amine to form an imine involves the reaction of a nitrile with diisobutylaluminum hydride; and then reacting the resultant compound with a primary or secondary amine to form the imine. The process is especially useful for producing enantiomerically pure chiral imines, and, ultimately, amines. Typical such imines have the formula: ##STR1## wherein R, R.sub.1, R.sub.2 and R.sub.3 are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, aryl and aralkyl.Type: GrantFiled: July 15, 1994Date of Patent: April 2, 1996Assignee: NPS Pharmaceuticals, Inc.Inventors: Bradford C. VanWagenen, Thomas E. D'Ambra
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Patent number: 5498796Abstract: A process for the preparation of amines by catalytic hydrogenation of nitriles in the presence of a nickel-containing support catalyst. The support catalyst contains Mg and Ni in coprecipitated form and in a molar ratio of 0.0075 to 0.075:1. There is 17 to 60 g of a water-insoluble support per mol of nickel, and 65% to 97% of the BET total surface area of the support catalyst is formed by pores having a radius r.sub.p .ltoreq.2.5 nm.Type: GrantFiled: April 19, 1995Date of Patent: March 12, 1996Assignee: Hoechst AktiengesellschaftInventors: Gregor Deckers, Dieter Frohning
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Patent number: 5493055Abstract: A process for the manufacture of para-phenetidine is described. The process comprises the following steps: (a) diazotizing para-phenetidine and coupling the resulting compound to phenol at a molar ratio of 1.3 to 1 phenol to the diazo compound;(b) ethylating the resulting compound at a temperature in the range of between 130.degree. C. to 200.degree. C., and (c) catalytically hydrogenating the ethylated compound, whereby two moles of para-phenetidine are produced, one of which being recycled as the starting reagent in the first step. The product obtained is of a high purity being substantially free from the undesired isomers.Type: GrantFiled: April 6, 1995Date of Patent: February 20, 1996Assignee: Tambour, Ltd.Inventor: Jacob Kalo
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Patent number: 5489710Abstract: A regioselective processes are disclosed for the synthesis of (1R,1S)-amino-(2S,2R)-alkanol, particularly (1R,1S)-amino-(2S,2R)-indanol.Type: GrantFiled: April 19, 1995Date of Patent: February 6, 1996Assignee: Merck & Co., Inc.Inventors: Thomas R. Verhoeven, F. Edward Roberts, Chris H. Senanayake, Kenneth M. Ryan
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Patent number: 5486609Abstract: A process for preparing carbocyclic m-aminohydroxyaromatics comprises reacting the corresponding o-- or m-halohydroxyaromatics or metal salts thereof with primary or secondary amines in the presence of a base and in the presence or absence of a diluent.Type: GrantFiled: March 24, 1995Date of Patent: January 23, 1996Assignee: BASF AktiengesellschaftInventors: Robert Reinhardt, Helmut Reichelt, Roland Merger
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Patent number: 5471002Abstract: A process for preparing trifluoromethylanilines of the formula (I), ##STR1## in which R.sup.1 and R.sup.2, independently of each other, are hydrogen, halogen, (C.sub.1 -C.sub.4) alkyl, hydroxyl, alkoxy, alkylthio, carboxyl, or a nitro or cyano group, by reacting compounds of the formula (II) ##STR2## in which X.sub.1, X.sub.2 and X.sub.3 are in each case, identically or differently, halogen atoms,a is 0 or 1,Y is fluorine, chlorine or bromine, andR.sup.1 and R.sup.2 have the defined meaning, with anhydrous hydrofluoric acid, and converting the resulting aniline hydrofluorides with a base into the free amines.Type: GrantFiled: August 18, 1994Date of Patent: November 28, 1995Inventors: Wolfgang Appel, Gunter Siegemund
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Patent number: 5463130Abstract: A process for the preparation of peralkylated amines of the general formula I ##STR1## in which R.sup.1, R.sup.2 denote C.sub.1 -C.sub.200 alkyl, C.sub.3 -C.sub.8 cycloalkyl, C.sub.4 -C.sub.20 alkylcycloalkyl, C.sub.4 -C.sub.20 cycloalkylalkyl, C.sub.2 -C.sub.20 alkoxyalkyl, aryl, C.sub.7 -C.sub.20 alkylaryl, C.sub.7 -C.sub.20 aralkyl, C.sub.2 -C.sub.8 hydroxyalkyl, C.sub.2 -C.sub.8 mercaptoalkyl, C.sub.8 -C.sub.20 phenoxyalkyl, C.sub.2 -C.sub.8 aminoalkyl, C.sub.2 -C.sub.8 (NHR.sup.4)alkyl, C.sub.2 -C.sub.8 (NR.sup.4 R.sup.5)alkyl or together form a saturated or unsaturated C.sub.2 -C.sub.6 alkylene chain optionally mono- to tri-substituted by C.sub.1 -C.sub.4 alkyl and optionally interrupted by oxygen or nitrogenX denotes a C.sub.2 -C.sub.20 alkylene or C.sub.2 -C.sub.20 alkenylene or C.sub.4 -C.sub.8 cycloalkylene chain optionally mono- to penta-substituted by R.sup.3, C.sub.1 -C.sub.8 alkyl, C.sub.1 -C.sub.8 alkoxy, C.sub.1 -C.sub.8 dialkylamino, phenoxy, diphenylamino and/or C.sub.2 -C.sub.Type: GrantFiled: February 28, 1995Date of Patent: October 31, 1995Assignee: BASF AktiengesellschaftInventors: Tom Witzel, Eberhard Fuchs, Horst Zimmermann
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Patent number: 5453542Abstract: The present invention is a method of preparing a 4,6-bisarylazoresorcinol comprising reacting an aryldiazonium salt and resorcinol in the presence of a base and a reaction medium containing water and a water-miscible solvent at a temperature in the range of about -5.degree. C to about -60.degree. C. The present invention is also a method of preparing a 2-substituted 4,6-bisarylazoresorcinol comprising reacting an aryldiazonium salt with a 2-substituted resorcinol. The 4,6-bisarylazoresorcinol or 2-substituted 4,6-bisarylazoresorcinol can then be hydrogenated to a 4,6-diaminoresorcinol, which is a precursor to polybisbenzoxazoles (PBOs), polymers which are useful as insulators, solar arrays, and tear-resistant gloves.Type: GrantFiled: February 24, 1994Date of Patent: September 26, 1995Assignee: The Dow Chemical CompanyInventors: Ted A. Morgan, Bassam S. Nader, Paul Vosejpka, Weshi Wu, Andrew S. Kende
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Patent number: 5451702Abstract: A process for preparing substituted aromatic amines is provided which comprises contacting a nucleophilic compound and an azo containing compound in the presence of a suitable solvent system, reacting the nucleophilic compound and the azo containing compound in the presence of a suitable base and a controlled amount of protic material at a temperature of about 10.degree. C. to about 150.degree. C. in a confined reaction zone wherein the molar ratio of protic material to base is 0:1 to about 5:1 and reducing the product of the reaction of the nucleophilic compound and the azo containing compound under conditions which produce the substituted aromatic amine. In another embodiment, the substituted aromatic amines of the invention are reductively alkylated to produce alkylated diamines or substituted derivatives thereof.Type: GrantFiled: April 26, 1993Date of Patent: September 19, 1995Assignee: Monsanto CompanyInventors: Michael K. Stern, Brian K-M Cheng
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Patent number: 5449830Abstract: A regioselective processes are disclosed for the synthesis of (1R,1S)-amino-(2S,2R)-alkanol, particularly (1R,1S)-amino-(2S,2R)-indanol.Type: GrantFiled: March 11, 1994Date of Patent: September 12, 1995Assignee: Marck & Co., Inc.Inventors: Thomas R. Verhoeven, Edward F. Roberts, Chris H. Senanayake, Kenneth M. Ryan
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Patent number: 5442118Abstract: A method for the enantioselective reduction of an .alpha.-iminoketone to an .alpha.-aminoalcohol is disclosed. The method utilizes a borane reducing agent as the reducing agent and a chiral 1,3,2-oxazaborole as the catalyst. The method is applied to the synthesis of R-albuterol from methyl 5-acetylsalicylate in high yield and high optical purity.Type: GrantFiled: April 22, 1994Date of Patent: August 15, 1995Assignee: Sepracor, Inc.Inventors: Yun Gao, Yaping Hong, Charles M. Zepp
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Patent number: 5436371Abstract: A process for preparing p-nitroaromatic amides is provided which comprises contacting a nitrile, nitrobenzene, a suitable base and water in the presence of a suitable solvent system to form a mixture, and reacting the mixture at a suitable temperature in a confined reaction zone in the presence of a controlled amount of protic material. The p-nitroaromatic amides of the invention can be reduced to p-aminoaromatic amides. In one embodiment, the p-aminoaromatic amide is further reacted with ammonia under conditions which produce the corresponding p-aminoaromatic amine and the amide corresponding to the nitrile starting material or with water in the presence of a suitable basic or acidic catalyst under conditions which produce the corresponding p-aminoaromatic amine and the acid or salt thereof corresponding to the nitrile starting material. In another embodiment, the p-aminoaromatic amine is reductively alkylated to produce alkylated p-aminoaromatic amine.Type: GrantFiled: August 29, 1994Date of Patent: July 25, 1995Assignee: Monsanto CompanyInventors: Michael K. Stern, Brian K. Cheng