Preparing Esters By Carbonylation Patents (Class 560/175)
  • Patent number: 11773048
    Abstract: A process is provided for the preparation of value added chemicals such as ethyl levulinate from a glucose or other sugars, catalyzed by a mixture of a Lewis acid catalyst and a Bronsted acid catalyst.
    Type: Grant
    Filed: January 15, 2020
    Date of Patent: October 3, 2023
    Assignee: Council of Scientific & Industrial Research
    Inventors: Vijay Bokade, Prashant Niphadkar
  • Patent number: 10315979
    Abstract: Preparation of 2,5,6-trihydroxy-3-hexenoic acid and 2,5-dihydroxy-3-pentenoic acid and esters thereof from C6 and C5 sugars in the presence of a Lewis Acid material, wherein the yield of the 2,5,6-trihydroxy-3-hexenoic acid or 2,5-dihydroxy-3-pentenoic acid or esters thereof exceeds 15%.
    Type: Grant
    Filed: June 20, 2016
    Date of Patent: June 11, 2019
    Assignee: HALDOR TOPSØE A/S
    Inventors: Esben Taarning, Irantzu Sadaba Zubiri, Sebastian Meier
  • Patent number: 9073966
    Abstract: The present invention relates to a method for screening compounds having the ability to prevent, suppress or reduce malodor development on body surfaces. In particular, the method allows to efficiently screen for compound having the ability of preventing sweat malodor development caused by volatile sulfur compounds (VSCs). The present invention is based on the finding of the direct precursor of naturally VSCs, which is present in human sweat and which will be metabolized by Staphylococci to VSCs.
    Type: Grant
    Filed: May 30, 2012
    Date of Patent: July 7, 2015
    Assignee: Firmenich SA
    Inventors: Christian Starkenmann, Anthony Clark, Myriam Troccaz, Yvan Niclass
  • Publication number: 20150126765
    Abstract: Compounds of the formula (I) wherein R2, A are certain substituents, Y is an ester group, a nitrile group or an amido group and Z is O, S or N?R2, and which compounds are, for example, useful as intermediates for pyrazole fungicides, can be prepared by the reaction of a compound of formula R2—C(O)—CH2Y, with an orthoformate HC—(OR3)3 in the presence of a base, especially in the presence of an amine, e.g.
    Type: Application
    Filed: May 7, 2013
    Publication date: May 7, 2015
    Inventor: Janis Jaunzems
  • Publication number: 20150045576
    Abstract: Unique methods have been developed to convert saccharides into value-added products such as alkyl lactates, lactic acid, alkyl levulinates, levulinic acid, and optionally alkyl formate esters and/or hydroxymethylfurfural (HMF). Useful catalysts include Lewis acid catalysts and Brønsted acid catalysts including mineral acids, metal halides, immobilized heterogeneous catalysts functionalized with a Brønsted acid group or a Lewis acid group, or combinations thereof. The saccharides are contacted with the catalyst in the presence of various alcohols.
    Type: Application
    Filed: August 6, 2014
    Publication date: February 12, 2015
    Inventors: Herman P. Benecke, Daniel Garbark
  • Patent number: 8299293
    Abstract: A method for preparing ?-keto acids, especially ?-ketomethionine, and/or derivatives thereof, whereby an aldehyde is reacted with thiols to give a corresponding dithioacetal, the dithioacetal formed, is reacted with an electrophile in the presence of a strong base, and the resulting ?,?-(dithio)carboxylic acid is solvolyzed with acid-catalysis to release thiol and give the ?-keto acid or a derivative thereof. Umpolung of aliphatic or aromatic aldehydes is effected by reaction with thiols.
    Type: Grant
    Filed: July 9, 2008
    Date of Patent: October 30, 2012
    Assignee: Evonik Degussa GmbH
    Inventors: Christoph Kobler, Martin Hateley, Philipp Roth, Barbara Jaeger, Christoph Weckbecker, Klaus Huthmacher
  • Patent number: 7566782
    Abstract: The present invention relates to a process for the preparation of rosuvastatin calcium, a promising new HMG-CoA reductase inhibitor.
    Type: Grant
    Filed: December 10, 2002
    Date of Patent: July 28, 2009
    Assignee: Ranbaxy Laboratories Limited
    Inventors: Yatendra Kumar, Hashim Nizar Poovanathil Nagoor Meeran, Shantanu De, Mohammad Rafeeq, Swargam Sathyanarayana
  • Patent number: 7268250
    Abstract: A highly efficient process is provided for producing an optically active compound having high optical purity by an asymmetric reaction using as a catalyst a transition metal complex having an optically active nitrogen-containing compound as an asymmetric ligand.
    Type: Grant
    Filed: December 31, 2003
    Date of Patent: September 11, 2007
    Assignee: Kanto Kagaku Kabushiki Kaisha
    Inventors: Masahito Watanabe, Kunihiko Murata, Takao Ikariya
  • Patent number: 7265240
    Abstract: A process for the carbonylation of ethylenically unsaturated compounds is described. The process comprises reacting an ethylenically unsaturated compound with carbon monoxide in the presence of a source of hydroxyl groups and a catalyst system. The catalyst system is obtained by combining: (a) metal of Group VIII or a compound thereof; and (b) a bidentate phosphine of general formula (I) The carbonylation reaction is carried out at a temperature of between ?30° C. to 49° C. and under a CO partial pressure of less than 30×105 N.
    Type: Grant
    Filed: August 4, 2003
    Date of Patent: September 4, 2007
    Assignee: Lucite International UK Limited
    Inventors: Graham R. Eastham, Cristina Jimenez, David Cole-Hamilton
  • Patent number: 6946582
    Abstract: The present invention provides a process for producing a fluoroalkyl iodide represented by the general formula (II): Rf-CH2CH2I??(II) wherein Rf is a perfluoroalkyl or polyfluoroalkyl group comprising 1 to 20 carbons, the process comprising reacting hydrogen iodide gas with a fluoroalkene in the presence of a catalyst. The present invention also provides a process for producing a fluoroester by reacting the fluoroalkyl iodide with a carboxylate.
    Type: Grant
    Filed: November 20, 2002
    Date of Patent: September 20, 2005
    Assignee: Daikin Industries, Ltd.
    Inventors: Toshiyuki Katsube, Kouzou Noda, Jun Miki
  • Patent number: 6541660
    Abstract: A process is proposed for preparing C5 acetate for Vitamin A synthesis by hydroformylation of 3,4-diacetoxybut-1-ene (3,4-DABE), according to which a 3,4-DABE is used which is obtained by acetoxylation of 1,3-butadiene with acetic acid and air in the presence of a catalyst and removing by distillation the 3,4-DABE formed in this case as by-product.
    Type: Grant
    Filed: March 27, 2002
    Date of Patent: April 1, 2003
    Assignee: BASF Aktiengesellschaft
    Inventors: Udo Rheude, Maximilian Vicari, Werner Aquila, Günter Wegner, Jörg Niekerken
  • Patent number: 6515161
    Abstract: A hydroformylation process is disclosed which employs multidentate phosphite ligands in a catalyst composition. In particular, the ligands have heteroatom-containing substituents on the carbon attached to the ortho position of the terminal phenol group.
    Type: Grant
    Filed: August 30, 2000
    Date of Patent: February 4, 2003
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: Kristina Ann Kreutzer, Wilson Tam, John Ronald Boyles, J Michael Garner
  • Patent number: 6465680
    Abstract: A process for preparing a malonic acid monoester or &bgr;-ketoester from an epoxide includes the steps of reacting an epoxide with carbon monoxide and an alcohol in the presence of a catalytic amount of a cobalt compound and at least one promoter to produce a &bgr;-hydroxyester, separating the &bgr;-hydroxyester from the cobalt compound and the promoter, and oxidizing the &bgr;-hydroxyester to produce a malonic acid monoester or &bgr;-ketoester.
    Type: Grant
    Filed: June 20, 2001
    Date of Patent: October 15, 2002
    Assignee: Samsung Electronics Co., Ltd.
    Inventors: Byeong No Lee, In-Sun Jung, Eun Joo Jang
  • Patent number: 6452043
    Abstract: A method for producing esters, carboxylic acids and mixtures thereof includes contacting, under carbonylation conditions, lower alkyl alcohols, ethers, lower alkyl alcohol derivatives and mixtures thereof and carbon monoxide with a catalyst having a catalytically effective amount a metal selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, tin and mixtures thereof associated with a carbonized polysulfonated divinylbenzene-styrene copolymer matrix. In a preferred aspect of the invention the method is called out under vapor-phase conditions.
    Type: Grant
    Filed: April 5, 2000
    Date of Patent: September 17, 2002
    Assignee: Eastman Chemical Company
    Inventors: Joseph Robert Zoeller, Andy Hugh Singleton, Gerald Charles Tustin, Donald Lee Carver
  • Publication number: 20020052531
    Abstract: Supported bis(phosphorus) ligands are disclosed for use in hydroformylation reactions, including the hydroformylation of olefins. Catalysts are formed when the ligands are complexed with a catalytically active metal (e.g., rhodium or iridium).
    Type: Application
    Filed: February 16, 2001
    Publication date: May 2, 2002
    Inventors: Emilio E. Bunel, Patrick M. Burke, Joy D. Druliner, Leo E. Manzer, Kenneth G. Moloy, Manxue Wang
  • Publication number: 20020035290
    Abstract: A process for preparing a malonic acid monoester or &bgr;-ketoester from an epoxide includes the steps of reacting an epoxide with carbon monoxide and an alcohol in the presence of a catalytic amount of a cobalt compound and at least one promoter to produce a &bgr;-hydroxyester, separating the &bgr;-hydroxyester from the cobalt compound and the promoter, and oxidizing the &bgr;-hydroxyester to produce a malonic acid monoester or &bgr;-ketoester.
    Type: Application
    Filed: June 20, 2001
    Publication date: March 21, 2002
    Applicant: Samsung Electronics Co., Ltd.
    Inventors: Byeong No Lee, In-Sun Jung, Eun Joo Jang
  • Patent number: 5932761
    Abstract: It is provided a process for industrially advantageously producing a branched aldehyde represented by the formula; ##STR1## ?wherein Y represents an acyl group of two or more carbon atoms; and X represents an acyloxymethyl group represented by --CH.sub.2 OY' (where Y' represents an acyl group of two or more carbon atoms), cyano group or an alkoxycarbonyl group! which is useful as an intermediate for pharmaceuticals and agricultural chemicals, comprising subjecting an olefinic compound represented by the following formula; ##STR2## (wherein Y and X are the same as defined above), to the reaction with hydrogen and carbon monoxide in the presence of a rhodium compound and a tertiary organic phosphorus compound with an electronic parameter (.upsilon.-value) of 2080 to 2090 cm.sup.-1 or with a steric parameter (.theta.-value) of 150 to 180.degree..
    Type: Grant
    Filed: March 23, 1998
    Date of Patent: August 3, 1999
    Assignee: Kuraray Co., Ltd.
    Inventors: Toshihiro Omatsu, Masahiko Kitayama, Takashi Onishi
  • Patent number: 5670700
    Abstract: A hydroformylation process for the production of 5-formylvaleric acid from 2-, or 3-pentenoic acid, or 5-formylvaleric acid ester from 2-, or 3-pentenoic acid ester, or 5-formylvaleronitrile from 2-, or 3-pentenenitrile by reaction with hydrogen and carbon monoxide in a solvent containing a catalyst having a platinum component, a bidentate diaryl phosphine component, an acid promoter component.
    Type: Grant
    Filed: August 25, 1995
    Date of Patent: September 23, 1997
    Assignees: E. I. Du Pont de Nemours and Company, DSM, N.V.
    Inventors: Patrick Michael Burke, Onko Jan Gelling, Henk Oevering, Imre Toth
  • Patent number: 5585524
    Abstract: Method for the preparation of an aldehyde in a process in which cobalt is being recycled by:(a) hydroformylating of an ethylenically unsaturated compound with carbon monoxide and hydrogen at a pressure higher than 5 MPa and a temperature higher than 80.degree. C. in the presence of a cobalt carbonyl compound in an organic phase, following which(b) removing cobalt from the organic phase by contacting the organic phase with a polar mixture, which mixture is substantially immiscible with the organic phase, first the pressure being reduced to a pressure lower than 5 MPa and simultaneously or afterwards cooling being applied down to a temperature below 80.degree. C.
    Type: Grant
    Filed: June 23, 1995
    Date of Patent: December 17, 1996
    Assignee: DSM N.V.
    Inventors: Otto E. Sielcken, Nicolaas F. Haasen
  • Patent number: 5527950
    Abstract: The invention relates to a process for the preparation of a 5-formylvalerate ester by hydroformylating a mixture of pentenoate esters in the presence of a catalyst system which catalyst system comprises a metal from group 8-10 of the Periodic Table of Elements and a mono- or multidentate organic phosphorous ligand, wherein the mixture of pentenoate esters contains less than 500 ppm hydroperoxide compounds.
    Type: Grant
    Filed: December 28, 1994
    Date of Patent: June 18, 1996
    Assignees: DSM N.V., E.I. Du Pont de Nemours & Co.
    Inventors: Carolina B. Hansen, Antonius J. J. M. Teunissen
  • Patent number: 5436356
    Abstract: A process for the carbonylation of ethylenically unsaturated compounds by reaction with carbon monoxide and a co-reactant in the presence of a substantially non-acidic catalyst system based on a palladium compound and a bidentate ligand of the formulaR.sub.1 R.sub.2 M.sub.1 RM.sub.2 R.sub.3 R.sub.4in which M.sub.1 and M.sub.2 may be phosphorus, arsenic or antimony atom, R is a bivalent organic bridging group, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently substituted or non-substituted aliphatic groups, with the proviso that R.sub.1 together with R.sub.2, and/or R.sub.3 together with R.sub.4 form a bivalent cyclic group with at least 5 ring atoms whereby the two free valencies are linked to M.sub.1 or M.sub.2, respectively.Catalytic compositions employing the bidentate ligands used in this method in which M.sub.1 and M.sub.2 are phosphorous are also presented.
    Type: Grant
    Filed: January 14, 1994
    Date of Patent: July 25, 1995
    Assignee: Shell Oil Company
    Inventors: Eit Drent, Dennis H. L. Pello, Melis Hasselaar
  • Patent number: 5264616
    Abstract: .omega.-Formyl-C.sub.4 -C.sub.20 -alkanecarboxylic esters are prepared by reacting C.sub.4 -C.sub.20 -alkenecarboxylic esters with carbon monoxide and hydrogen at from 30.degree. to 150.degree. C. and under from 0.01 to 30 bar in the presence of rhodium carbonyl complexes which are modified with polyphosphites.
    Type: Grant
    Filed: February 17, 1993
    Date of Patent: November 23, 1993
    Assignee: BASF Aktiengesellschaft
    Inventors: Michael Roeper, Peter M. Lorz, Dieter Koeffer
  • Patent number: 5237097
    Abstract: 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: Grant
    Filed: December 22, 1992
    Date of Patent: August 17, 1993
    Assignee: Quantum Chemical Corporation
    Inventors: David W. Smith, Ronnie M. Hanes
  • Patent number: 5107015
    Abstract: The preparation of 2-formyl-2-methyl succinates by reacting itaconates with carbon monoxide and hydrogen in contact with a catalyst system comprising rhodium and a tertiary phosphorus compound, wherein the reaction is carried out under a pressure of from 90 to 325 bar.
    Type: Grant
    Filed: October 24, 1990
    Date of Patent: April 21, 1992
    Assignee: BASF Aktiengesellschaft
    Inventors: Werner Bertleff, Gerhard Butz
  • Patent number: 5091559
    Abstract: A process is disclosed for forming alkyl 4-oxobutyrates and its acetals which comprises reacting under anhydrous conditions acrolein or its acetals with carbon monoxide and an alcohol of the formula R OH wherein R is lower alkyl in the presence of a catalytically effective amount of a catalyst comprising palladium metal which is either unsupported or supported on an inert carrier and a promoting effective amount of hydrogen halide. An intermediate in the process, i.e., .beta.-halopropionaldehyde or acetal thereof can also be used in forming alkyl 4-oxobutyrates and acetals thereof by reacting under anhydrous conditions said .beta.-halopropionaldehyde or its acetals with carbon monoxide and an alcohol of the formula ROH wherein R is lower alkyl in the presence of a catalytically effective amount of a catalyst comprising palladium metal which is either unsupported or supported on an inert carrier.
    Type: Grant
    Filed: February 8, 1988
    Date of Patent: February 25, 1992
    Assignee: Quantum Chemical Corporation
    Inventors: Jawad H. Murib, William D. Baugh
  • Patent number: 5072005
    Abstract: Methyl 4-oxobutyrate and its methanol addition products, methyl 4,4-dimethoxybutyrate and gamma-methoxy-gamma-butyrolactone, which are useful as intermediates in the preparation of such industrially important compounds as gamma-butyrolactone, 1,4-butanediol and glutamic acid, are produced from the reaction of acrolein, carbon monoxide and methanol in the presence of a catalyst system which consists of (a) a Group VIII metal component selected from palladium metal or a palladium-containing composition which generates palladium metal under reaction conditions, (b) a hydrogen halide and (c) an arylarsine catalyst copromoter.
    Type: Grant
    Filed: July 9, 1987
    Date of Patent: December 10, 1991
    Assignee: National Distillers and Chemical Corporation
    Inventors: Jawad H. Murib, William D. Baugh
  • Patent number: 4950429
    Abstract: 6-Aminocaproic acid is prepared by(a) reacting a 5-formylvaleric acid ester with water in the presence of an acid agent at 30.degree.-200.degree. C. and(b) reacting the 5-formylvaleric acid thus obtained with excess ammonia and hydrogen in the presence of a hydrogenation catalyst and of a solvent which is inert under the reaction conditions at 50.degree.-150.degree. C. under superatmospheric pressure.
    Type: Grant
    Filed: March 23, 1989
    Date of Patent: August 21, 1990
    Assignee: BASF Aktiengesellschaft
    Inventors: Uwe Vagt, Rolf Fischer, Franz Merger, Hans-Martin Hutmacher
  • Patent number: 4945179
    Abstract: Process for the preparation of esters of carboxylic acids by contacting an olefinically unsaturated compound with CO and an alcohol, in the presence of (a) a ruthenium compound and (b) an iodide salt, LiBr and/or an onium bromide, with a molar ratio of CO to olefinically unsaturated compound.ltoreq.2.0 being applied when "b" is an iodide salt.
    Type: Grant
    Filed: August 15, 1988
    Date of Patent: July 31, 1990
    Assignee: Shell Oil Company
    Inventor: Eit Drent
  • Patent number: 4849542
    Abstract: A process for the preparation of oxo-alkanedioic acids or diesters thereof by reacting an alkenoic acid or an ester thereof, at least one of the C atoms of the carbon carbon double bond carrying a H atom, with CO and H.sub.2 in the presence of a catalytic system prepared by combining:a. Pd and/or a Pd compound,b. a compound containing an anion of an acid having a pKa of less than 2, except hydrohalogenic acid and carboxylic acids, andc. a bidentate ligandR.sup.1 R.sup.2 --M--R--M--R.sup.3 R.sup.4wherein M is P, As or Sb, R is a divalent organic bridging group having at least two C atoms in the bridge, and R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are optionally substituted hydrocarbon groups.
    Type: Grant
    Filed: October 28, 1986
    Date of Patent: July 18, 1989
    Assignee: Shell Oil Company
    Inventor: Eit Drent
  • Patent number: 4849543
    Abstract: This invention concerns a process for the production of diesters by hydroformylation/Michael addition of alkyl acrylates, which comprises contacting the alkyl acrylate with carbon monoxide and hydrogen in the presence of a catalyst system comprising a rhodium-containing compound, excess phosphine-containing ligand, a nitrogen-containing compound and a solvent at a temperature of 70.degree.-150.degree. C. and a pressure of 500-4000 psi.
    Type: Grant
    Filed: November 15, 1985
    Date of Patent: July 18, 1989
    Assignee: Texaco Inc.
    Inventor: Jiang-Jen Lin
  • Patent number: 4837356
    Abstract: Methyl-4-ketohexanoate is prepared by reacting methyl acrylate, ethylene, carbon monoxide and a secondary alcohol, e.g. a secondary alcohol having 3 to 20 carbon atoms, in the presence of a catalyst comprising a complex combination of rhodium, carbon monoxide and triorganophosphorus.
    Type: Grant
    Filed: October 23, 1987
    Date of Patent: June 6, 1989
    Assignee: Shell Oil Company
    Inventor: Kuo-Hua Chao
  • Patent number: 4664851
    Abstract: Process for the co-production of carboxylic acids of the general formula R.sup.1 --COOH and R.sup.2 --COOH and carboxylic acid esters of the general formula R.sup.1 --COOCH.sub.2 R.sup.2 and R.sup.2 --COOCH.sub.2 R.sup.1 from carboxylic acid esters of the general formula R.sup.1 --COOR.sup.2 and/or ethers of the general formula R.sup.3 OR.sup.4 (R.sup.1, R.sup.2, R.sup.3, R.sup.4 representing (substituted) alkyl or (substituted) aryl, alkaryl or aralkyl, R.sup.1 also representing H), carbon monoxide and hydrogen at elevated temperature and pressure in the presence of a ruthenium compound, a further Group VIII metal compound, and a compound R.sup.5 Hal or R.sup.5 COHal where R.sup.5 has one of the meanings given for R.sup.2 and Hal is iodine or bromine, the reaction mixture being substantially free from other transistion metal or Group II metal iodides or bromides, and containing a trivalent nitrogen compound containing a group ##STR1## (X=O or S), such as an amide, a carbamate, a urea or a derivative thereof.
    Type: Grant
    Filed: July 19, 1982
    Date of Patent: May 12, 1987
    Assignee: Shell Oil Company
    Inventor: Eit Drent
  • Patent number: 4647691
    Abstract: Ethyl and n-propyl esters of carboxylic acids are prepared in good yield from methanol, syngas and a carboxylic acid by contacting a mixture of the carboxylic acid, carbon monoxide, hydrogen and methanol with a catalyst composition comprising a ruthenium-containing compound, a cobalt-containing compound and a quaternary onium salt or base, and heating the resulting mixture at an elevated temperature and pressure for sufficient time to produce the desired ethyl and propyl esters, and then recovering the same from the reaction mixture.
    Type: Grant
    Filed: January 13, 1982
    Date of Patent: March 3, 1987
    Assignee: Texaco Inc.
    Inventors: Jiang-Jen Lin, John F. Knifton
  • Patent number: 4640802
    Abstract: Process for the co-production of carboxylic acids of the general formula R.sup.1 --COOH and R.sup.2 --COOH and carboxylic acid esters of the general formula R.sup.1 --COOCH.sub.2 R.sup.2 and R.sup.2 --COOCH.sub.2 R.sup.1 from carboxylic acid esters of the general formula R.sup.1 --COOR.sup.2 and/or ethers of the general formula R.sup.3 OR.sup.4 (R.sup.1, R.sup.2, R.sup.3, R.sup.4 representing (substituted) alkyl or (substituted) aryl, alkaryl or aralkyl, R.sup.1 also representing H), carbon monoxide and hydrogen at elevated temperature and pressure in the presence of a ruthenium compound, a further Group VIII metal compound, a phosphine oxide and a compound R.sup.5 Hal or R.sup.5 COHal where R.sup.5 has one of the meanings given for R.sup.2 and Hal is iodine or bromine, the reaction mixture being substantially free from other transition metal or Group II metal iodides or bromides, and containing a tertiary phosphine oxide.
    Type: Grant
    Filed: July 7, 1982
    Date of Patent: February 3, 1987
    Assignee: Shell Oil Company
    Inventor: Eit Drent
  • Patent number: 4545934
    Abstract: Process for the production of 4-substituted acetoacetic acid derivatives. An acetoacetic acid derivative having the formula: ##STR1## wherein R is alkoxy having 1 to 6 C atoms, phenoxy, --NR'.sub.2, wherein R' is alkyl having 1 to 6 C atoms or aryl, or NR'.sub.2, which is azetidine, pyrrolidine or piperidine, is treated with a secondary amine at an elevated temperature and in the presence of an organic solvent. The water formed is separated. The intermediate is converted into the corresponding 3-enamine carboxylic acid derivative. The derivative is converted by treatment with sodium amide in liquid ammonia into the corresponding sodium salt. The sodium salt is converted by treatment with a halogen compound having the formula R.sub.1 CH.sub.2 X or R.sub.1 R.sub.2 CHX, wherein R.sub.1 and R.sub.2 each are alkyl, alkenyl, alkinyl or aryl and X is chlorine, bromine or iodide, into the corresponding 4-substituted enamino derivative. The derivative is hydrolyzed into the 4-substituted acetoacetic acid derivative.
    Type: Grant
    Filed: March 21, 1984
    Date of Patent: October 8, 1985
    Assignee: Lonza Ltd.
    Inventors: Felix Previdoli, Leander Tenud
  • Patent number: 4518793
    Abstract: Disclosed is a process for preparing an acetone dicarboxylic acid diester, which comprises allowing diketene, carbon monoxide and a nitrous acid ester to react in the presence of a palladium halide or a complex thereof.
    Type: Grant
    Filed: October 17, 1983
    Date of Patent: May 21, 1985
    Assignee: UBE Industries, Ltd.
    Inventors: Shinichiro Uchiumi, Kikuo Ataka
  • Patent number: 4360692
    Abstract: An improved process for the preparation of alkyl formylvalerates, wherein butadiene or a butadiene-containing hydrocarbon mixture is reacted, in a first stage, with carbon monoxide and alkanols in the presence of cobalt carbonyl complexes and, per mole of butadiene, from 0.5 to 2 moles of tertiary nitrogen bases having a pK.sub.a of from 3 to 11, at from 80.degree. to 150.degree. C. and from 300 to 2,000 bar, and, in a second stage, the resulting alkyl pentenoate is reacted with carbon monoxide and hydrogen in the presence of cobalt carbonyl complexes at from 100.degree. to 160.degree. C.
    Type: Grant
    Filed: November 10, 1980
    Date of Patent: November 23, 1982
    Assignee: BASF Aktiengesellschaft
    Inventors: Rudolf Kummer, Heinz-Walter Schneider
  • Patent number: 4334042
    Abstract: In the carbonylation of olefinic compounds in the presence of a cobalt carbonyl catalyst, the addition to the reaction system of a secondary phosphine oxide represented by the general formula ##STR1## wherein R.sup.1 and R.sup.2 are the same or different and each is substituted or unsubstituted hydrocarbon residue having not more than about 20 carbon atoms, in an amount of 0.2 to 20 moles per gram atom of the cobalt makes it possible to separate the reaction product from the reaction mixture by direct distillation without any such special operation for the catalyst separation as required in the conventional processes. The distillation residue which contains the catalyst can be recycled for the reuse thereof in the carbonylation.
    Type: Grant
    Filed: July 23, 1979
    Date of Patent: June 8, 1982
    Assignee: Kuraray Co. Ltd.
    Inventors: Mitsuo Matsumoto, Masuhiko Tamura
  • Patent number: 4255591
    Abstract: There is provided an improved continuous homogeneous catalytic carbonylation process wherein a mixed gas stream is removed from the carbonylation reactor, condensable liquids separated from said gas stream and said gas stream vented, the improvement comprising contacting said gas stream with a plurality of hollow fiber membranes selectively permeable to hydrogen under conditions substantially non-degrading of the membranes to generate a non-permeated gas stream of higher carbon monoxide content and recycling said non-permeated gas stream to the carbonylation process reactor. There is also provided for the recovery and recycle to the process of carbonylation products such as acetic or propionic acids by adsorption and removal from a solid adsorbent or absorption in a liquid absorbent.
    Type: Grant
    Filed: November 20, 1978
    Date of Patent: March 10, 1981
    Assignee: Monsanto Company
    Inventors: Earle C. Makin, Jerry L. Price, Yu W. Wei
  • Patent number: 4209467
    Abstract: A hydroformylation process in which the catalyst is the reaction product of a cobalt carbonyl compound with a nitrogen-containing heterocyclic compound having an enolic hydroxyl group on the carbon atom adjacent to the ring-forming nitrogen atom or the catalyst is the reaction product of a .beta.-dioxo cobalt compound and a nitrogen-containing base having a double bonded carbon atom at the .alpha.-position, with carbon monoxide and hydrogen.
    Type: Grant
    Filed: January 2, 1979
    Date of Patent: June 24, 1980
    Assignee: Daicel Ltd.
    Inventors: Hidetaka Kojima, Shingo Oda, Takushi Yokoyama, Yasukazu Murakami
  • Patent number: 4052461
    Abstract: The invention relates to a process for the preparation of aldehydes by the hydroformylation of olefinically unsaturated compounds using a rhodium catalyst which catalyst is provided by (1) introducing rhodium into the reaction solution in the form of an ionic rhodium compound, the said ionic compound consisting of (a) a rhodium-containing cation having rhodium complexed with ligands other than halide, and (b) a non-coordinating anion; and (2) furnishing to the reaction solution at least two moles of a modifying ligand per mole of ionic rhodium compound where the modifying ligand is furnished either pre-coordinated in the said ionic rhodium compound or as a free compound, and where the modifying ligand is a tertiary organo phosphorous compound having from 3 to 90 carbon atoms, or a tertiary organo arsenic compound having from 3 to 90 carbon atoms, or a tertiary organo antimony compound having from 3 to 90 carbon atoms.
    Type: Grant
    Filed: April 4, 1975
    Date of Patent: October 4, 1977
    Assignee: Monsanto Company
    Inventors: Harold Burnham Tinker, Donald E. Morris