Preparation By Carbonylation Patents (Class 562/406)
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Patent number: 6121500Abstract: A mixture of water and a glycol, such as ethylene glycol, is employed as the solvent for the reaction between 1,6-dibromo-2-naphthol and an alkali metal sulfite in the preparation of 6-bromo-2-naphthol and its derivatives to effect a substantial reduction in reaction time. The glycol/water mol ratio is ordinarily in the range of 0.1-0.5/1, preferably 0.3/0.5/1.Type: GrantFiled: March 4, 1999Date of Patent: September 19, 2000Assignee: Albemarle CorporationInventor: Mahmood Sabahi
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Patent number: 6114550Abstract: A .beta.-phenylisoserine derivative of general formula (I): ##STR1## in the form of a salt or an ester, in which Ar represent an aryl radical, R represents a phenyl or naphthyl or a O--R.sub.1 radical and G.sub.1 represents --CH.sub.2 --Ph radical; and a method of using the same for making taxane derivatives.Type: GrantFiled: November 10, 1997Date of Patent: September 5, 2000Assignee: Rhone-Poulenc Rorer S.A.Inventors: Jean-Noel Denis, Andrew-Elliot Greene, Alice Kanazawa
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Patent number: 6096920Abstract: Palladium-catalyzed arylation of an olefin (e.g., ethylene) with an aromatic halide (e.g., 2-bromo-6-methoxynaphthalene, m-bromobenzophenone, or 4-isobutyl-1-bromobenzene) is conducted in specified media. After a special acid or base phase separation procedure, palladium-catalyzed carbonylation of the olefinically-substituted aromatic intermediate is conducted in specified media using CO and water or an alcohol to form arylalkylcarboxylic acid or ester or substituted arylalkylcarboxylic acid or ester (e.g., racemic 2-(6-methoxy-2-naphthyl)propionic acid, 2-(3-benzoylphenyl)propionic acid, or 2-(4-isobutylphenyl)propionic acid). Catalyst recovery procedures enabling recycle of catalyst residues and efficient recovery of amine hydrogen halide scavenger and solvent used in the arylation reaction are described, as well as novel, highly efficient methods of conducting the carbonylation reaction.Type: GrantFiled: July 8, 1998Date of Patent: August 1, 2000Assignee: Albemarle CorporationInventors: Robert H. Allen, R. Carl Herndon, Jr., Kannappan C. Chockalingam, W. Dirk Klobucar, Gary D. Focht, Tse-Chong Wu, Gary D. Heidebrecht, Joseph D. McLean, Yaping Zhong, Thorsten W. Brockmann, Ronny W. Lin, William J. Layman, Jr., Ranjit K. Roy
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Patent number: 6093847Abstract: The present invention relates to an process for the preparation of ibuprofen, which comprises reacting para isobutyl phenylethanol (p-IBPE), a halide source, a protonic acid, water and the catalyst which is a compound having formula 1 which is shown herebelow: ##STR1## Wherein M = a group VIII metal specifically palladium or platinum,R.sub.1, R.sub.2, R.sub.3 = substituents on the phosphine ligand such as hydrogen, alkyl, aryl, arylalkyl cycloaliphatic,X = groups such as aryl or alkyl sulphonato or aryl or alkyl carboxylato ort formato or halides such as CI.sup.-, Br.sup.-, I.sup.-, ##STR2## = a semilabile anionic chelating ligand containing a donor and an O.sup.Type: GrantFiled: March 31, 1999Date of Patent: July 25, 2000Assignee: Council of Scientific and Industrial ResearchInventors: Raghunath V. Chaudhari, Seayad A. Majeed, Jayasree Seayad
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Patent number: 6080888Abstract: Arylolefinic compounds are prepared by reacting aryl halide with an olefinic compound in the presence of a polar liquid reaction medium containing (a) secondary or tertiary amine as a hydrogen halide acceptor (b) a catalyst system formed from (i) Pd or Pd(0) compound, and/or Pd(I) salt or Pd(II) salt, and (ii) a tertiary phosphine ligand, and (c) a reaction accelerating amount of water in the range of about 0.5 to about 5 weight percent of the total weight of the reaction mixture. The arylolefinic compounds can be converted to an arylcarboxylic acid by hydrocarboxylation with CO in a reaction medium freed of amine and containing water and a Pd catalyst system as above in which a copper component may be included, and which preferably includes an ether such as THF.Type: GrantFiled: January 8, 1997Date of Patent: June 27, 2000Assignee: Albemarle CorporationInventors: Tse-Chong Wu, Kannappan C. Chockalingham, W. Dirk Klobucar, Gary D. Focht
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Patent number: 5922901Abstract: It is contemplated to provide an industrially adapted method for producing a dimerization product of acrylonitrile, which method is capable of producing a straight chain dimer of acrylonitrile efficiently at a high yield in a simple manner using a highly active catalyst exhibiting superior stability, without suffering from occurrence of difficulty removable by-products. In the method according to the present invention, acrylonitrile is subjected to dimerization in the presence of a ruthenium complex composed of a central atom of ruthenium and ligands including cyclopentadiene or its derivative coordinating thereto. The dimerization product, such as adiponitrile, 1,4-dicyanobutene or 1,4-dicyanobutadiene, is useful as an intermediate for producing hexamethylenediamine and adipic acid, both serving for the starting material of nylon 66, or as an intermediate for producing, for example, an antirusting agent and a vulcanization accelerator for rubbers.Type: GrantFiled: February 26, 1997Date of Patent: July 13, 1999Assignee: Mitsui Chemicals, Inc.Inventors: Yasuhiko Suzuki, Yoshihisa Kiso
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Patent number: 5902898Abstract: The activity of a palladium catalyst in the carboxylation of an aralkene with carbon monoxide and water or an alcohol in the absence of oxygen can be enhanced when it is used in conjunction with (A) a ligand mixture comprising compounds corresponding to the formulas R.sub.3 ZY and R'.sub.3 Z wherein each R and R' is independently selected from alkyl, aryl and substituted aryl groups; Y is a member of Group VIA of the Periodic Table; and Z is an element having a Pauling electronegativity of 1.9-2.5 or (B) a complex ligand providing all of the elements of said mixture. The invention has particular utility in carboxylating an aralkene such as 4-isobutylstyrene or 2-methoxy-6-vinylnaphthalene to ibuprofen or naproxen or their esters; and the preferred novel ligand is usually a 50/50 mixture of phosphine and phosphine oxide.Type: GrantFiled: February 26, 1998Date of Patent: May 11, 1999Assignee: Albemarle CorporationInventor: Tse-Chong Wu
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Patent number: 5808142Abstract: A process for the preparation of 2-hydroxynaphthalene-6-carboxylic acid using potassium carbonate and CO at temperatures above 260.degree. C. and at a pressure of at least 10 bar comprises using 2-hydroxynaphthalene-3-carboxylic acid and/or 2-hydroxynaphthalene-3,6-dicarboxylic acid and/or their potassium salts and, if desired, potassium .beta.-naphtholate as starting materials.The process according to the invention enables a considerable increase, by reusing the secondary products, in the product selectivity with regard to 2-hydroxy-naphthalene-6-carboxylic acid.Type: GrantFiled: September 13, 1994Date of Patent: September 15, 1998Assignee: Hoechst AktiengesellschaftInventors: Siegbert Rittner, Hans-Martin Ruffer, Jorg Schmid, Thomas Wisser
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Patent number: 5756853Abstract: The subject of the present invention is a process for the preparation of a 4-hydroxybenzaldehyde carrying at least one substituent in the position ortho to the OH group.It more particularly relates to the preparation of 3-methoxy-4-hydroxybenzaldehyde and of 3-ethoxy-4-hydroxybenzaldehyde.The process for the preparation of a substituted 4-hydroxybenzaldlehyde, substituted at least in the 3 position by an alkoxy group, is characterized in that it comprises subjecting a substituted phenol compound, substituted at least in the 2 position by an alkoxy group and in which the 4 and 6 positions are free, to a first stage of carboxylation in the 6 position, then to a stage of hydroxymethylation in the 4 position, followed by a stage of oxidation of the hydroxymethyl group to a formyl group, and finally to a last decarboxylation stage.Type: GrantFiled: October 16, 1996Date of Patent: May 26, 1998Assignee: Rhone-Poulenc ChimieInventors: Pascal Metivier, Isabelle Jouve, Christian Maliverney
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Patent number: 5726346Abstract: This invention relates to a method of stereoselective preparation of a derivative of .beta.-phenylisoserine of formula (I) by the action of an N-carbonyl-benzylimine of formula (II) on an optically active amide of a protected hydroxyacetic acid of formula (III), followed by hydrolysis of the product obtained. In formula (I), (II) or (III), R is an optionally substituted phenyl radical or R.sub.1 --O, Ar is an optionally substituted aryl radical and G.sub.1 is a hydroxy function protection grouping. The product of formula (I) is particularly useful in preparing taxol and Taxotere which have remarkable antitumor properties.Type: GrantFiled: April 5, 1995Date of Patent: March 10, 1998Assignee: Rhone-Poulenc Rorer S.A.Inventors: Jean-Noel Denis, Andrew-Elliot Greene, Alice Kanazawa
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Patent number: 5650537Abstract: A process for the preparation of N-acylglycine derivatives of the formula (I) ##STR1## which comprises reacting a carboxylic acid amide with an aldehyde in the presence of a solvent and an acid to give an acylaminomethylol and then carbonylating the acylaminomethylol in the presence of a cobalt carbonyl catalyst.Type: GrantFiled: May 2, 1995Date of Patent: July 22, 1997Assignee: Hoechst AGInventors: Matthias Beller, Hartmut Fischer, Thomas Gerdau, Peter Gross
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Patent number: 5639894Abstract: A process for the carbonylation of allylic alcohols such as nerolidol, farnesol, or their monocyclic analogues with carbon monoxide at a pressure of at least 30 bar in the presence of a polar solvent and a palladium halide catalyst, optionally an alkali metal halide salt, and optionally an alcoholic solvent. The carbonylated product may then be reduced to the corresponding alcohol, which is cyclized in the presence of Lewis or Bronsted acids to afford an ambergris fragrance compound.Type: GrantFiled: March 23, 1994Date of Patent: June 17, 1997Assignee: Henkel Kommanditgesellschaft auf AktienInventors: Jonathan M. Cassel, Steven M. Hoagland, James M. Renga
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Patent number: 5631393Abstract: The invention relates to palladium compounds containing as ligands compounds of the formula (I) ##STR1## where Ar is C.sub.6 H.sub.4 SO.sub.3 M, M is hydrogen, ammonium, a monovalent metal or one equivalent of a polyvalent metal and Ph is the phenyl radical and n, m are zero, 1 or 2 and x, y, u, v are zero, 1 or 2.Type: GrantFiled: May 2, 1995Date of Patent: May 20, 1997Assignee: Hoechst AktiengesellschaftInventors: Christian Kohlpaintner, Matthias Beller
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Patent number: 5536870Abstract: A process for preparing olefin compounds of the formula ##STR1## where A is aryl, substituted aryl, heteroaryl, substituted heteroaryl, benzyl, substituted benzyl, vinyl or substituted vinyl and R.sub.2, R.sub.3 and R.sub.4 are hydrogen, alkyl, cycloalkyl, alkyl-substituted cycloalkyl, aryl, substituted aryl, alkoxy, alkythio, heteroaryl, substituted heteroaryl, alkanoyl, aroyl, substituted aroyl, heteroarylcarbonyl, substituted heteroarylcarbonyl, trifluoromethyl or halo, which comprises reacting an organic halide of the formula A-X where X is chloro, bromo or iodo with a vinyl or substituted vinyl compound of the formula ##STR2## where R.sub.2, R.sub.3 and R.sub.Type: GrantFiled: February 17, 1995Date of Patent: July 16, 1996Assignee: Albemarle CorporationInventor: Tse-Chong Wu
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Patent number: 5536874Abstract: There is provided a process for preparing an arylacetic acid or arylpropionic acid divative from an arylcarbinol which comprises the step of subjecting said arylcarbinol to suitable carbonylation conditions for a sufficient period of time and under suitable pressure and temperature to form said acid derivative, with the proviso that said carbonylation conditions include conducting the reaction in a two-phase system wherein one phase is an aqueous medium which contains (1) a catalyst which is a water-soluble metal complex consisting essentially of a Group VIII metal and a hydrophilic ligand such as palladium complexed with trisulfonated triphenylphosphine, and (2) optionally an acid, and wherein the second phase comprises said arylcarbinol.Type: GrantFiled: November 30, 1994Date of Patent: July 16, 1996Assignee: Hoechst Celanese CorporationInventors: Roger A. Sheldon, Leendert Maat, Georgios Papadogianakis
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Patent number: 5482596Abstract: A new process for preparing aryl substituted aliphatic carboxylic acids and their esters is provided. A 1-aryl substituted olefinic compound is reacted with carbon monoxide in the presence of water (in aqueous conditions) or an alcohol (in anhydrous conditions) at a temperature between about 25.degree. C. and about 200.degree. C. An excess of several moles of water or of anhydrous alcohol is preferred. An acid such as hydrochloric acid may also be added. As catalyst, a mixture of a palladium compound and optionally a copper compound with a ligand mixture comprising a compound of the formula (R').sub.3 ZY and a compound of the formula (R").sub.3 Z where each R' and R" are the same or different and is alkyl, aryl or substituted aryl, and Z is any atom that has a Pauling electronegativity of between 1.9 and 2.5 and Y is a member of Group VIA of the Periodic Table of Elements.Type: GrantFiled: January 27, 1994Date of Patent: January 9, 1996Assignee: Albemarle CorporationInventor: Tse-Chong Wu
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Patent number: 5430181Abstract: Process for improving a controlled oxidation reaction between at least one reactant and oxygen, in which at least one reactant is reacted with oxygen or an oxygen containing gas, constituting a reaction mixture, in the presence of at least one additional gas which is introduced into said reaction mixture and is selected from methane, ethane and helium, and the resulting reaction product from the oxidation reaction is possibly treated so as to give a final product.Type: GrantFiled: February 19, 1993Date of Patent: July 4, 1995Assignee: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation des Procedes Georges ClaudeInventors: Philippe Arpentinier, Jacques Koenig, Yves Torre
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Patent number: 5416237Abstract: In a process for the production of acetic acid by carbonylation of methanol in the presence of a rhodium carbonylation catalyst, methyl iodide and an iodide salt stabiliser the improvement resides in maintaining a finite concentration of water of up to about 10% by weight and a methyl acetate concentration of at least 2% by weight in the liquid reaction composition and recovering the acetic acid product by passing the liquid reaction composition through a flash zone to produce a vapour fraction which is passed to a single distillation column from which an acetic acid product is removed.Type: GrantFiled: July 18, 1994Date of Patent: May 16, 1995Assignee: BP Chemicals LimitedInventors: Simon D. Aubigne, Jeremy B. Cooper, Bruce L. Williams, Derrick J. Watson
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Patent number: 5399747Abstract: A new process for preparing aryl-substituted aliphatic carboxylic acids is provided. Aryl-substituted aliphatic ether or thioether compound is reacted with carbon monoxide in aqueous conditions at a temperature between about 25.degree. C. and about 200.degree. C. An acid such as hydrochloric acid may be added. As catalyst, a mixture of palladium or a palladium compound and a copper compound with at least one acid-stable ligand are present.Type: GrantFiled: January 27, 1994Date of Patent: March 21, 1995Assignee: Albemarle CorporationInventors: Kannappan Chockalingam, Tse-Chong Wu
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Patent number: 5360938Abstract: This invention relates to asymmetric syntheses in which a prochiral or chiral compound is contacted in the presence of an optically active metal-ligand complex catalyst to produce an optically active product.Type: GrantFiled: July 16, 1992Date of Patent: November 1, 1994Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: James E. Babin, Gregory T. Whiteker
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Patent number: 5344960Abstract: A cobalt based catalyst, and the method for preparing it, are disclosed. The catalyst is obtained from the reaction between NaCo(CO).sub.4 and s-trichloro triazine and is advantageously used in the processes of carbonylation of naphthalene mono- and disulfonates in order to yield naphthalene esters and acids.Type: GrantFiled: December 6, 1993Date of Patent: September 6, 1994Assignee: Enichem S.p.A.Inventors: Giuseppe Cometti, Annick Du Vosel, Franco Francalanci, Roberto Santi
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Patent number: 5344961Abstract: An improved process for the carbonylation of aryl halides comprises contacting the aryl halide with carbon monoxide under carbonylation conditions in the presence of a co-reactant, a base, and a catalyst system formed from a source of palladium and a bidentate phosphine ligand wherein at least one monovalent phosphorus substituent is aromatic and is substituted on at least one aromatic ring carbon atom with an electron-withdrawing group.Type: GrantFiled: May 27, 1993Date of Patent: September 6, 1994Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 5324750Abstract: Cyclodextrin derivatives and inclusion complexes having increased solubility and stability are provided. Cyclodextrin derivatives include amino and other modified cyclodextrins, and linked cyclodextrins. Inclusion complexes comprising the foregoing cyclodextrins, and processes for making the cyclodextrin derivatives are disclosed. Also disclosed are cyclodextrin derivatives comprising otherwise substituted or unsubstituted cyclodextrins covalently bonded to agents such as pharmaceuticals. The covalent bond, when broken, yields the agent in active form. Pharmaceutical compositions and methods of treating an animal host are also described, as well as chromatographic compositions and a method for separating racemic mixtures.Type: GrantFiled: November 20, 1992Date of Patent: June 28, 1994Assignee: Australia Commercial Research & Development LimitedInventors: Stephen F. Lincoln, John H. Coates, Christopher J. Easton, Stephen J. Van Eyk, Bruce L. May, Paramjit Singh, Michael L. Williams, Martyn A. Stile
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Patent number: 5322959Abstract: A new process for preparing aryl substituted aliphatic carboxylic acid esters is provided. A 1-aryl substituted aliphatic halo compound is reacted with carbon monoxide in the presence of an alcohol in anhydrous conditions at a temperature between about 25.degree. C. and about 200.degree. C. An excess of several moles of anhydrous alcohol is preferred. An acid such as hydrochloric acid may also be added. As catalyst, a mixture of palladium or a palladium compound and a copper compound with at least one acid-stable ligand are present.Type: GrantFiled: May 11, 1993Date of Patent: June 21, 1994Assignee: Ethyl CorporationInventor: Tse-Chong Wu
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Patent number: 5315026Abstract: A catalytic process for preparing aryl substituted aliphatic carboxylic acid esters is disclosed. A 1-aryl substituted olefinic compound is reacted with carbon monoxide in the presence of an alcohol in anhydrous conditions at a temperature between about 25.degree. C. and about 200.degree. C. An excess of several moles of anhydrous alcohol is preferred. An acid such as hydrochloric acid may also be added. As catalyst, a mixture of a palladium compound and a copper compound is used with at least one acid-stable cyclic phosphine having the formula: ##STR1## where R' is the same or different than R" and is alkyl or aryl, said aryl, either substituted or unsubstituted, and Ar' is phenyl, naphthyl, substituted phenyl or substituted naphthyl and n is an integer from 3 to 6.Type: GrantFiled: September 29, 1993Date of Patent: May 24, 1994Assignee: Ethyl CorporationInventor: Tse-Chong Wu
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Patent number: 5315027Abstract: A process for preparing alkyl esters of ibuprofen is provided. A 1-halo-1-(4-isobutylphenyl)ethane is reacted in an anhydrous medium with carbon monoxide in the presence of an alkoxide source at a temperature between about 10.degree. C. and about 200.degree. C. An excess of several moles of alcohol is preferred. An acid such as hydrogen chloride may also be added. As catalyst, a palladium compound having at least one acid-stable ligand is present; however, an excess of ligand over palladium is advantageous.Type: GrantFiled: May 11, 1993Date of Patent: May 24, 1994Assignee: Ethyl CorporationInventors: Thanikavelu Manimaran, Tse-Chong Wu, Felix M. Orihuela
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Patent number: 5315028Abstract: A new process for preparing aryl substituted aliphatic carboxylic acid esters is provided. A 1-aryl substituted olefinic compound is reacted with carbon monoxide in the presence of an alcohol in anhydrous conditions at a temperature between about 25.degree. C. and about 200.degree. C. An excess of several moles of anhydrous alcohol is preferred. An acid such as hydrochloric acid may also be added. As catalyst, a mixture of a palladium compound and a copper compound with at least one acid-stable ligand are present.Type: GrantFiled: May 12, 1993Date of Patent: May 24, 1994Assignee: Ethyl CorporationInventor: Tse-Chong Wu
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Patent number: 5315029Abstract: A new process for preparing alkyl esters of ibuprofen is provided. A 1-halo-1-(4-isobutylphenyl)ethane is reacted with carbon monoxide in the presence of an anhydrous alcohol at a temperature between about 10.degree. C. and about 200.degree. C. An excess of several moles of alcohol is preferred. An acid such as trifluoroacetic acid is also added. As catalyst, a palladium compound and at least one acid-stable ligand over palladium are present; however, an excess of ligand over palladium is advantageous.Type: GrantFiled: May 11, 1993Date of Patent: May 24, 1994Assignee: Ethyl CorporationInventor: Kannappan Chockalingam
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Patent number: 5315030Abstract: A new process for preparing aliphatic carboxylic acid esters is provided. A substituted aliphatic ether or thioether compound is reacted with carbon monoxide in the presence of an alcohol in anhydrous conditions at a temperature between about 25.degree. C. and about 200.degree. C. An excess of several moles of anhydrous alcohol is preferred. An acid such as hydrochloric acid may also be added. As catalyst, a mixture of palladium or a palladium compound and a copper compound with at least one acid-stable ligand are present.Type: GrantFiled: September 29, 1993Date of Patent: May 24, 1994Assignee: Ethyl CorporationInventors: Kannappan Chockalingam, Tse-Chong Wu
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Patent number: 5312975Abstract: A process for the preparation of 5-(2,4-difluorophenyl)-salicylic acid comprising the reaction of an organometallic derivative with a suitable substituted benzene in the presence of a transition-metal based catalyst is described.Type: GrantFiled: December 27, 1991Date of Patent: May 17, 1994Assignee: Zambon Group S.p.A.Inventors: Claudio Giordano, Laura Coppi, Francesco Minisci
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Patent number: 5288900Abstract: This invention relates to certain salts of leukotriene antagonists and the use of certain amines to form these salts as a means for selectively crystallizing optical isomers of the leukotriene antagonists recited herein.Type: GrantFiled: April 22, 1993Date of Patent: February 22, 1994Assignee: Smithkline Beecham CorporationInventors: Trevor Laird, Robert J. Mills
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Patent number: 5281751Abstract: A process for the production of an aliphatic carboxylic acid of the formula RCOOH, wherein R is an alkyl group having from 1 to 5 carbon atoms, comprises the catalytic reaction of an alcohol of formula ROH and carbon monoxide in the presence of a rhodium catalyst, methyl iodide, a high lithium iodide content, a low water content and an organic ester of formula RCO.sub.2 R. The process can optionally be carried out in the presence of hydrogen and/or an organic ligand of formula ER.sup.11.sub.3 where E is nitrogen, phosphorus, arsenic, antimony or bismuth and R.sup.11 is an organic moiety.Type: GrantFiled: December 29, 1992Date of Patent: January 25, 1994Assignee: Union Carbide Chemicals and Plastics Company Inc.Inventor: David J. Schreck
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Patent number: 5278335Abstract: A new process for preparing alkyl esters of ibuprofen is provided. A 1-halo-1-(4-isobutylphenyl)ethane is reacted with carbon monoxide in the presence of an anhydrous alcohol at a temperature between about 10.degree. C. and about 200.degree. C. An excess of several moles of alcohol is preferred. An acid such as trifluoroacetic acid is also added. As catalyst, a mixture of a copper compound and a palladium or a palladium compound and at least one acid-stable ligand are present.Type: GrantFiled: June 11, 1993Date of Patent: January 11, 1994Assignee: Ethyl CorporationInventor: Kannappan Chockalingam
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Patent number: 5260477Abstract: A method for preparing .alpha.-(4-isobutylphenyl)propionic acid or its precursor is here disclosed which comprises a step (I) of dehydrogenating p-isobutylethylbenzene in a gaseous phase in the presence of a dehydrogenating metal catalyst to form p-isobutylstyrene and at least one unsaturated hydrocarbon compound selected from a group A defined in Claim 1; a step (II) of reacting p-isobutylstyrene obtained in the step (I) with carbon monoxide and hydrogen or with carbon monoxide and water or a lower alcohol in the presence of a transition metal complex carbonylating catalyst to form .alpha.-(4-isobutylphenyl)propionic acid or its precursor; and a step (III) of hydrogenating at least one unsaturated hydrocarbon compound selected from the group A obtained in the dehydrogenation step (I) to form p-isobutylethylbenzene, and recycling the thus formed p-isobutylethylbenzene through the step (I) as the raw material of the step (I).Type: GrantFiled: December 18, 1989Date of Patent: November 9, 1993Assignee: Nippon Petrochemicals Co., Ltd.Inventors: Isoo Shimizu, Yasuo Matsumura, Yuichi Tokumoto, Kazumichi Uchida
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Patent number: 5254720Abstract: A new process for preparing aryl substituted aliphatic carboxylic acids or then alkyl esters is provided. A 1-aryl substituted olefin is reacted with carbon monoxide in the presence of water or an alcohol at a temperature between about 25.degree. C. and about 200.degree. C. An excess of several moles of water or alcohol is preferred. An acid such as hydrochloric acid may also be added. As catalyst, a mixture of a palladium compound and a copper compound with at least one acid-stable ligand are present.Type: GrantFiled: December 28, 1992Date of Patent: October 19, 1993Assignee: Ethyl CorporationInventor: Tse-Chong Wu
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Patent number: 5237097Abstract: A process is disclosed for the carbonylation of an organic compound selected from the group consisting of an olefin, an alcohol, an acid and an ester. In this process the organic compound is reacted with carbon monoxide in the presence of a Group VIII metal-containing catalyst. The liquid carbonylation product solution of this reaction is conveyed to a separation zone maintained at a lower total pressure than is the pressure in the reaction zone. Simultaneously with the conveyance of the liquid product solution to the separation zone is the introduction therein of a carbon monoxide-containing gaseous stream, the carbon monoxide therein contributing a partial pressure of up to 30 psia of the total pressure in said separation zone. A portion of the liquid carbonylation product solution is flashed and removed from the separation zone. The unflashed liquid carbonylation product solution is recycled back into the reaction zone.Type: GrantFiled: December 22, 1992Date of Patent: August 17, 1993Assignee: Quantum Chemical CorporationInventors: David W. Smith, Ronnie M. Hanes
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Patent number: 5202477Abstract: A process for the production of an aliphatic carboxylic acid of the formula RCOOH, wherein R is an alkyl group having from 1 to 5 carbon atoms, comprises the catalytic reaction of an alcohol of formula ROH and carbon monoxide in the presence of a rhodium catalyst, methyl iodide, a high lithium iodide content, a low water content and an organic ester of formula RCO.sub.2 R. The process can optionally be carried out in the presence of hydrogen and/or an organic ligand of formula ER.sup.11.sub.3 where E is nirogen, phosphorus, arsenic, antimony or bismuth and R.sup.11 is an organic moiety.Type: GrantFiled: June 5, 1990Date of Patent: April 13, 1993Assignee: Union Carbide Chemicals and Plastics Company Inc.Inventor: David J. Schreck
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Patent number: 5194631Abstract: A process for producing a carboxylic acid which comprises reacting an organic chloride having at least one chloride atom on its ring of a substituted or unsubstituted, aromatic or heterocyclic hydrocarbon with carbon monoxide in the presence of an inorganic base or an organic base and water at a reaction temperature of 150.degree. to 300.degree. C., and preferably 160.degree. to 300.degree. C., by using as catalysts a palladium compound and a phosphine compound represented by the general formula (III):(R).sub.2 P--X--P(R).sub.2 (III)wherein R is an alkyl group or a substituted or unsubstituted phenyl group, and X is an alkylene group having 1 to 6 carbon atoms, ##STR1## or a binaphthyl group.Type: GrantFiled: July 11, 1989Date of Patent: March 16, 1993Assignee: Nihon Nohyaku Co., Ltd.Inventors: Keiji Suto, Koji Nakasa, Masaaki Kudo, Moriharu Yamamoto
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Patent number: 5179224Abstract: Disclosed herein is a process for preparing a corresponding cinnamate ester by reacting a styrene compound, carbon monoxide, an alcohol and oxygen by the use of (1) metallic palladium or a compound thereof, (2) a copper compound, (3) a compound of at least one metal selected from Groups 4A, 5A, 7A, 8A (the iron group only) and 2B in the Periodic Table and (4) a halogen compound as a catalyst which comprises treating the catalyst components recovered from the reaction liquid after completion of the reaction with an oxidizing agent in the presence of an organic acid to regenerate their catalytic activity, using the resulting catalyst components again in the reaction as a catalyst and repeating the foregoing procedure.The regenerated catalyst is recovered in catalytic activity to the extent of that of a fresh catalyst and thus gives a high reaction performance in the subsequent reaction. Thus, the catalyst containing expensive metal can be used circulatively.Type: GrantFiled: October 1, 1991Date of Patent: January 12, 1993Assignee: Mitsui Toatsu Chemicals, IncorporatedInventors: Usaji Takaki, Yoshihiro Yamamoto, Toshio Matsuhisa, Isamu Sudo, Shinobu Aoki
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Patent number: 5179229Abstract: A process for the preparation of 2,2-diorgano-3-arylpropionic acids is disclosed by the carbonylation of corresponding 2,2-diorgano-1-aryl ethanol in the presence of a Lewis acid catalyst. Furthermore, a process for the production of 2,2-diorgano-3-arylpropionic esters is disclosed by reacting a corresponding 2,2-diorgano-1-aryl ethanol with carbon monoxide and an alcohol in the presence of a Lewis acid catalyst.Type: GrantFiled: April 24, 1992Date of Patent: January 12, 1993Assignee: Hoechst Celanese CorporationInventor: Varadaraj Elango
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Patent number: 5166418Abstract: A method is provided for the preparation of ibuprofen by carbonylating 1-(4'-isobutylphenyl)ethanol (IBPE) with carbon monoxide comprising initially a reaction mixture comprising IBPE, ibuprofen and a catalyst for the carbonylation with carbon monoxide under conditions to initiate the reaction, and continuing to feed carbon monoxide to the composition to produce the desired yield of ibuprofen. Preferably the catalyst comprises palladium and a monodentate phosphine ligand. The presence of ibuprofen in the feed composition when the reaction is initiated with CO makes it possible to obtain high selectivities to ibuprofen with substantially complete conversion of IBPE at much shorter reaction times than if no ibuprofen is present initially.Type: GrantFiled: December 4, 1991Date of Patent: November 24, 1992Assignee: Hoechst Celanese CorporationInventors: Joel D. Hendricks, Graham N. Mott
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Patent number: 5166419Abstract: A method for preparing .alpha.-(4-isobutylphenyl)propionic acid or its precursor is here disclosed which comprises the following steps (I), (II) and (III):step (I): subjecting isobutylbenzene and a polyalkylbenzene to disproportionation reaction in order to form p-isobutylethylbenzenestep (II): dehydrogenating p-isobutylethylbenzene obtained in the step (I) to form p-isobutylstyrene, andstep (III): the following step (IIIa) or (IIIb):step (IIIa): reacting p-isobutylstyrene obtained in the step (II) with carbon monoxide and hydrogen to prepare .alpha.-(4-isobutylphenyl)propionaldehyde, orstep (IIIb): reacting p-isobutylstyrene obtained in the preceding step (II) with carbon monoxide and water or a lower alcohol to prepare .alpha.-(4-isobutylphenyl)propionic acid or its alkyl ester.Type: GrantFiled: August 22, 1990Date of Patent: November 24, 1992Assignee: Nippon Petrochemicals Co., Ltd.Inventors: Yuuichi Tokumoto, Isoo Shimizu, Satoru Inoue
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Patent number: 5158921Abstract: A catalyst system, which containsa) a source of a group VIII metal, andb) a phosphine of general formula: ##STR1## in which R.sup.1, R.sup.2 and R.sup.3 are independently selected from an optionally substituted aryl group and a group of general formula: ##STR2## wherein eachh of A, X, Y and Z is independently selected from a nitrogen atom, a CH group and a group of formula CR wherein R represents a hydroxyl group, an amino group, an amido group, a cyano group, an aryl group, an aryloxy group, a halogen atom, an optionally substituted hydrocarbyl group or an optionally substituted hydrocarbyloxy group, it also being possible for two adjacent CR groups to form a ring, provided that at least one of R.sup.1, R.sup.2 and R.sup.3 represents a group of formula (II) in which at least one of A and Z represents a group of formula CR; or an acid addition salt thereof.Also disclosed is the use of the catalyst system in the selective carbonylation of unsaturated hydrocarbons.Type: GrantFiled: February 28, 1990Date of Patent: October 27, 1992Assignee: Shell Oil CompanyInventors: Eit Drent, Petrus H. M. Budzelaar, Willem W. Jager
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Patent number: 5149868Abstract: A process for the carbonylation of olefinically or alkynically unsaturated compounds with carbon monoxide in the presence of water and a catalyst, wherein the catalyst is based ona) a palladium compound,b) a phosphine general formula PR.sup.1 R.sup.2 R.sup.3, wherein R.sup.1, R.sup.2 and R.sup.3 are the same or different each represent an alkyl, cycloalkyl or aryl group, at least one of which carries a substituent selected from the group consisting of a sulphonic acid, phosphonic acid and carboxylic acid groups, or a salt thereof, andc) an anion of an acid having a pK.sub.a <3 (measured in water at 18.degree. C.) except hydrohalogenic acids,and wherein the reaction medium is at least initally a multiphase liquid reaction medium.Type: GrantFiled: March 19, 1991Date of Patent: September 22, 1992Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 5097061Abstract: A method for preparing .alpha.-(4-isobutylphenyl)propionic acid or its precursor is here disclosed which comprises a step A of forming p-isobutylstyrene from p-isobutylethylbenzene and a step B of forming .alpha.-(4-isobutylphenyl)propionaldehyde from p-isobutylstyrene or a step C of forming .alpha.-(4-isobutylphenyl)propionic acid or its alkyl ester from p-isobutylstyrene.Furthermore, a method for preparing said p-isobutylethylbenzene is also disclosed which comprises alkylating isobutylbenzene or 4-ethyltoluene with ethylene or propylene.Type: GrantFiled: June 19, 1989Date of Patent: March 17, 1992Assignee: Nippon Petrochemicals Co., Ltd.Inventors: Isoo Shimizu, Yasuo Matsumura, Yuuichi Tokumoto, Kazumichi Uchida
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Patent number: 5091563Abstract: A process for preparing an .alpha.-phenylpropionic acid derivative wherein an .alpha.-phenylethyl alcohol derivative is reacted with carbon monoxide in the presence of a catalyst to give an .alpha.-phenylpropionic acid derivative, which comprises carrying out the reaction in either one of the following manners (I), (II) and (III):(I) effecting said reaction in the presence of a rhodium catalyst, as said catalyst, together with an iodine compound in such an amount as to give a Rh to I ratio on an atomic basis of 1:0.5 to 1:6; adjusting the concentration of water in the reaction mixture to a level of 2 mol/l or below; and employing a reaction temperature of 130.degree. C.Type: GrantFiled: December 11, 1989Date of Patent: February 25, 1992Assignee: Daicel Chemical Industries, Ltd.Inventors: Yasutaka Tanaka, Hidetaka Kojima, Yasuo Tsuji
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Patent number: 5087731Abstract: A process of alkoxycarbonylation making use of a new catalyst consisting of a palladium-phosphine complex, the phosphine having a pKa greater than or equal to 7, a chlorinated aromatic compound, carbon monoxide and an alcohol.Type: GrantFiled: October 2, 1990Date of Patent: February 11, 1992Assignee: Rhone-Poulenc ChimieInventors: Marc Huser, John Osborn
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Patent number: 5081279Abstract: This invention provides a method of producing highly pure .alpha.-(3-benzoylphenyl)propionic acid derivatives, which are medicines per sec or which can easily afford the same, from readily available 3-ethylbenzophenone in a very simplified manner efficiently and economically. The method comprises dehydrogenating 3-ethylbenzophenone in vapor phase in the presence of an inert gas and carbonylating the formed 3-ethenylbenzophenone in the presence of a carbonylation catalyst comprising a transition metal complex.Type: GrantFiled: November 6, 1990Date of Patent: January 14, 1992Assignee: Nippon Petrochemicals Company, LimitedInventors: Isoo Shimizu, Yasuo Matsumura, Yoshihisa Inomata
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Patent number: 5081292Abstract: .beta., .gamma.-Unsaturated carboxylic acids, e.g., 3-hexene-1,6-dioic acid, are selectively prepared by carbonylating (with carbon monoxide) an allyl alcohol, e.g., a butenediol, at an elevated temperature and under superatmospheric pressure, in the presence of a catalytically effective amount of a palladium-based catalyst and at least one quaternary onium chloride of one of the Group VB elements nitrogen or phosphorus, such element being tetracoordinated via carbon atoms and with the proviso that such nitrogen atom may be coordinated to two pentavalent phosphorus atoms.Type: GrantFiled: April 30, 1990Date of Patent: January 14, 1992Assignee: Rhone-Poulenc ChimieInventors: Philippe Denis, Jean Jenck, Robert Perron
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Patent number: 5055611Abstract: A process for preparing ibuprofen is described. The improved process involves the treatment of spent palladium carbonylation catalyst with oxygen at about 300.degree. C. to about 850.degree. C. The treated material then used with a phosphine ligand to carbonylate 1-halo-1-(4-isobutyl-phenyl)ethane, 1-hydroxyl-1-(4-isobutylphenyl)ethane, or isobutylstyrene to produce ibuprofen.Type: GrantFiled: December 4, 1990Date of Patent: October 8, 1991Assignee: Ethyl CorporationInventors: Ronny W. Lin, R. Carl Herndon, Jr., E. E. Atkinson, Jr.