Preparing Alicyclic Acid Esters By Carbonylation Patents (Class 560/114)
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Patent number: 4973740Abstract: A process for producing a tricyclodecanecarboxylic acid ester by reacting dihydrodicyclopentadiene with CO and an alcohol in the presence of anhydrous HF is disclosed. The reaction is performed in a solvent at a temperature of from -20.degree. to 60.degree. C. under a CO partial pressure of from 5 to 50 atm. The alcohol is used in an amount of 0.7 to 5 moles per mole of the dihydrodicyclopentadiene. The anhydrous HF is used in an amount of at least 5 moles per mole of the dihydrodicyclopentadiene. The product tricyclodecanecarboxylic acid ester is useful as a flavor.Type: GrantFiled: September 28, 1989Date of Patent: November 27, 1990Assignees: Mitsubishi Gas Chemical Co., Inc., Kao CorporationInventors: Masami Ishihara, Takeshi Morokuma
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Patent number: 4960926Abstract: Process for the carbonylation of olefinically unsaturated compounds with carbon monoxide in the presence of a hydroxyl-group-containing compound, a palladium catalyst, an organic phosphine, an acid with a pKa value <2, with the exception of halogen acids and carboxylic acids as promoter, and a catlayst stabilizer selected from the group consisting of compounds of the general formula; ##STR1## wherein X represents an element of group Va with a valency greater than 3, selected from P. As or Sb, where Y represents an element of group VIa, selected from O, S or Se, and where either a, b and c are 0 or 1, where R.sub.4, R.sub.5 and R.sub.6 are the same or different and represent hydrocarbon groups, or a and b=0 and c=0 or 1 and R.sub.4 and R.sub.5 together with X form a heterocyclic group, or a, b and c=0 and R.sub.4, R.sub.5 R.sub.6 together with X form a heterocyclic group, compounds of the general formula: ##STR2## wherein R.sub.7 is a hydrocarbon group and where R.sub.8 and R.sub.Type: GrantFiled: July 27, 1989Date of Patent: October 2, 1990Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 4945179Abstract: 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: GrantFiled: August 15, 1988Date of Patent: July 31, 1990Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 4894188Abstract: Fatty acid and their derivatives are simply produced by reacting an olefin, carbon monoxide and water or reacting an alcohol or its derivative and carbon monoxide in the presence of a hydrogen fluoride catalyst and thermally decomposing the resulting reaction product in the presence of a lower hydrocarbon or a lower halogenated hydrocarbon.Type: GrantFiled: February 13, 1985Date of Patent: January 16, 1990Assignee: Mitsubishi Gas Chemical Company, Inc.Inventors: Takehiko Takahashi, Makoto Takagawa, Tomiyoshi Furuta, Toshio Hidaka, Kazuo Takada
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Patent number: 4795579Abstract: The invention relates to novel compounds usable as liquid crystals in liquid crystal display devices utilizing the electrically controlled birefringence effect.These compounds comply with formula: ##STR1## in which R.sup.1 represents an alkoxy or alkyl radical with 1 to 12 carbon atoms and Z represents a single bond or a radical chosen from among: ##STR2## provided that R.sup.1 represents an alkyl radical when Z represents a single bond and R.sup.2 represents an alkyl radical with 1 to 12 carbon atoms.They can be obtained by reacting an acid chloride of formula R.sup.Type: GrantFiled: February 26, 1987Date of Patent: January 3, 1989Assignee: Commissariat a l'Energie AtomiqueInventors: Claude Vauchier, Francoise Vinet
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Patent number: 4790963Abstract: A process for producing an ester is disclosed comprising contacting a gaseous reactant containing at least one organic hydroxy compound and a mixture of carbon monoxide and hydrogen with an ester synthesis catalyst of the formulaM.sub.a A.sub.b RuCu.sub.c N.sub.z O.sub.xwhereinM is selected from the group consisting of Ce, Cr, Fe, Mn and mixtures thereof,A is an alkali metal, alkaline earth metal or mixture thereof,a is from 0 to about 1,b is from 0.002 to about 10,c is from 0.2 to about 20,z is from 0 to about 196 by weight,x is the number of oxygens needed to fulfill the valence requirements of the other elements.The organic hydroxy compound can be provided separately or formed by contacting a mixture of carbon monoxide and hydrogen with an alcohol synthesis catalyst at an elevated temperature and pressure. The alcohol synthesis catalyst and ester synthesis catalyst can be in tandem or mixed.Type: GrantFiled: August 20, 1984Date of Patent: December 13, 1988Assignee: The Standard Oil CompanyInventors: Thomas G. Attig, Anne M. Graham, Frederick A. Pesa
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Patent number: 4739109Abstract: Process for the carbonylation of an acetylenically unsaturated compound with CO in the presence of an alcohol and/or water and of a catalyst formed by combining a Pd(II) compound, an organic phosphine and a protonic acid, with the exception of hydrohalogenic acids.Type: GrantFiled: November 27, 1985Date of Patent: April 19, 1988Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 4739107Abstract: Process for the preparation of dicarboxylate esters by reacting an optionally substituted ethylenically unsaturated hydrocarbon having two carbon atoms less than said dicarboxylic acid, CO and an alcohol in the presence of a Group VIII noble metal or a compound thereof, a quinone and optionally, a redox agent and molecular oxygen.Type: GrantFiled: January 12, 1987Date of Patent: April 19, 1988Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 4733006Abstract: The present invention provides for an improved process wherein an olefin, an alcohol, or an ester, halide or ether derivative of said alcohol is reacted with carbon monoxide in a liquid phase in the presence of a catalyst system that contains (a) a rhodium component, and (b) and iodine or bromine component. By passing at least a portion of the liquid reaction mass from the reaction zone to a separation zone of substantially lower CO partial pressure, at least a portion of the carbonylation products, as well as unreacted carbon monoxide, inert gases and unreacted olefin, alcohol or alcohol derivatives are vaporized and can be withdrawn from the separation zone. Precipitation of the rhodium catalyst under carbon monoxide deficient conditions is prevented or retarded by addition to the carbon monoxide deficient zones of the system of a catalyst stabilizer which is a germanium (IV) compound, an alkali metal compound, and mixtures thereof.Type: GrantFiled: August 18, 1983Date of Patent: March 22, 1988Assignee: Monsanto CompanyInventors: Thomas C. Singleton, Frank E. Paulik
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Patent number: 4705806Abstract: Prostacyclin (PGI.sub.2) analogs having a 6a-carba feature, for example a compound of the formula ##STR1## said analogs having pharmacological activity. Processes for preparing them and the appropriate intermediates are disclosed.Type: GrantFiled: February 13, 1978Date of Patent: November 10, 1987Inventor: Douglas R. Morton, Jr.
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Patent number: 4681707Abstract: Carboxylic acid esters are produced by reacting an unsaturated hydrocarbon, for example an olefin or an alkyne, with carbon monoxide and an alcohol in the presence of a protonic acid and as catalyst (a) at least one of the metals palladium, rhodium, ruthenium, iridium and cobalt, and (b) copper. In a modification of the invention carboxylic acids are produced by omitting the alcohol reactant and replacing it with water in an amount up to 8 mole equivalents based on the unsaturated hydrocarbon and a solvent other than an alochol, for example tetrahydrofuran.Type: GrantFiled: April 23, 1984Date of Patent: July 21, 1987Assignee: The British Petroleum Company p.l.c.Inventors: Howard Alper, Bertrand Despeyroux, David J. H. Smith, James B. Woell
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Patent number: 4670582Abstract: Process for the preparation of carboxylate esters of alpha-ethylenically unsaturated alcohols by reacting an ethylenically unsaturated compound with carbon monoxide and an enolizable ketone in the presence of a catalytic system formed by combining a palladium catalyst, a triarylphosphine and a protonic acid having a pK.sub.a below 1.5, except hydrohalogenic acids and carboxylic acids.Type: GrantFiled: August 15, 1986Date of Patent: June 2, 1987Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 4665213Abstract: Carboxylic acid esters are produced by reacting an olefinic hydrocarbon with an ester of formic acid in the presence of both carbon monoxide and oxygen at a temperature of up to 200.degree. and a pressure of up to 300 bar in the presence of water, typically in an amount of from 0.01 to 5% w/w, a source of protons, which is preferably a mineral acid or a tectometallosilicate in the hydrogen form, and as catalyst (a) a source of palladium, and (b) a source of copper.Type: GrantFiled: August 25, 1986Date of Patent: May 12, 1987Assignee: The British Petroleum Company p.l.c.Inventors: Howard Alper, David J. H. Smith
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Patent number: 4664851Abstract: 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: GrantFiled: July 19, 1982Date of Patent: May 12, 1987Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 4656307Abstract: According to the invention a derivative of brendane is provided. The derivative of brendane is represented by the general formula of: ##STR1## wherein R is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R.sup.1 to R.sup.3 each represent a hydrogen atom or a methyl group. The brendane derivative is prepared by reacting an alkenylnorbornene of the general formula of: ##STR2## wherein R.sup.1 to R.sup.3 each represent a hydrogen atom or a methyl group, with carbon monoxide and an alcohol or water in the presence of a catalyst of Group VIII metal compound of the periodic table.Type: GrantFiled: July 15, 1985Date of Patent: April 7, 1987Assignee: Nippon Oil Co., Ltd.Inventors: Yoshihiro Kobori, Tetsuya Takezono
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Patent number: 4649214Abstract: Norbornane-2-carboxylic acid esters are disclosed, in particular the 5(6)-formyl and the 5(6)-hydroxymethylnorbornane-2-carboxylic acid esters. The 5(6)-hydroxymethyl-norbornane-2-carboxylic acid esters may be reacted with polyols to provide a di- or polyfunctional polyol ester suitable for further reaction with polyisocyanates to prepare polyurethanes.Type: GrantFiled: November 30, 1984Date of Patent: March 10, 1987Assignee: Henkel CorporationInventors: Elizabeth J. Gladfelter, Edgar R. Rogier
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Patent number: 4647691Abstract: 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: GrantFiled: January 13, 1982Date of Patent: March 3, 1987Assignee: Texaco Inc.Inventors: Jiang-Jen Lin, John F. Knifton
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Patent number: 4642371Abstract: Preparation of a diester of a dicarboxylic acid by reacting an unsaturated hydrocarbon having two carbon atoms less than the dicarboxylic acid, carbon monoxide and a nitrite ester with a solvent in the presence of a catalyst system formed by combining (1) a Group VIII noble metal compound and (2) a vanadium salt and/or a titanium salt.Type: GrantFiled: May 14, 1986Date of Patent: February 10, 1987Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 4628113Abstract: A process for the preparation of carboxylic acids, alcohols, aldehydes or the secondary products thereof which comprises reacting an alcohol having from one to about twenty carbon atoms with hydrogen and carbon monoxide in the presence of a heterogeneous sulfided catalyst comprising cobalt in admixture with a co-catalyst selected from the elements of Groups V-B, VI-B and the Actinide series of the Periodic Table.Type: GrantFiled: June 30, 1982Date of Patent: December 9, 1986Assignee: Chevron Research CompanyInventor: Steven P. Current
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Patent number: 4628114Abstract: A process for the conversion of carboxylic acid esters to homologous carboxylic acid esters which comprises reacting a carboxylic acid ester having from two to about twenty carbon atoms with hydrogen and carbon monoxide in the presence of a heterogeneous sulfided catalyst comprising nickel, optionally in admixture with a co-catalyst selected from the elements of Group VI-B of the Periodic Table.Type: GrantFiled: June 23, 1983Date of Patent: December 9, 1986Assignee: Chevron Research CompanyInventor: Steven P. Current
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Patent number: 4625051Abstract: A process for the conversion of carboxylic acid esters to homologous carboxylic acid esters which comprises reacting a carboxylic acid ester having from two to about twenty carbon atoms with hydrogen and carbon monoxide in the presence of a heterogeneous sulfided catalyst comprising cobalt, optionally in admixture with a co-catalyst selected from the elements of Group VI-B of the Periodic Table.Type: GrantFiled: June 23, 1983Date of Patent: November 25, 1986Assignee: Chevron Research CompanyInventor: Steven P. Current
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Patent number: 4625055Abstract: A carboxylic acid, such as propionic acid, is prepared by carbonylation of an olefin, such as ethylene in the presence of water by the use of a molybdenum-nickel-alkali metal, tungsten-nickel alkali metal, or chromium-nickel-alkali metal co-catalyst in the presence of a halide.Type: GrantFiled: June 3, 1985Date of Patent: November 25, 1986Assignee: The Halcon SD Group, Inc.Inventor: Nabil Rizkalla
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Patent number: 4625049Abstract: A process for the preparation of carboxylic acids, alcohols, aldehydes or the secondary products thereof which comprises reacting an alcohol having from one to about twenty carbon atoms with hydrogen and carbon monoxide in the presence of a heterogeneous sulfided catalyst comprising nickel in admixture with a co-catalyst selected from the elements of Groups V-B, VI-B and the Actinide series of the Periodic Table.Type: GrantFiled: June 30, 1982Date of Patent: November 25, 1986Assignee: Chevron Research CompanyInventor: Steven P. Current
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Patent number: 4622416Abstract: A method is disclosed for the production of esters by reaction of an alkyl acyclic allylic ether such as 8-methoxy-1,6-octadiene with carbon monoxide in the presence of a halide of nickel, cobalt or iron as a catalyst and especially nickel iodide for the production of esters. Carbonylation of 8-methoxy-1,6-octadiene results in the production of methyl-3,8-nonadienoate; 2-(carbomethoxymethyl)-vinylcyclopentane; 2-(carbomethoxymethyl)-6-vinylcyclohexanone and 2-carbomethoxymethylbicyclo(3.3.0)-octan-3-one.Type: GrantFiled: April 19, 1985Date of Patent: November 11, 1986Assignee: National Distillers and Chemical CorporationInventors: Ronnie M. Hanes, William D. Baugh
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Patent number: 4588833Abstract: Substituted succinic acid amides, in particular substituted succinic acid amides containing differing derivative groups, are prepared by reacting unsaturated carboxamides with carbon monoxide and with a nucleophilic component containing at least one mobile hydrogen atom, in the presence of cobalt compounds and, if appropriate, in the presence of one or more tertiary nitrogen bases, under an elevated pressure and at an elevated temperature.Type: GrantFiled: October 26, 1984Date of Patent: May 13, 1986Assignee: Bayer AktiengesellschaftInventors: Jurgen Kadelka, Hans-Helmut Schwarz
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Patent number: 4585594Abstract: 4-Substituted but-3-ene-1-carboxylic acids and their esters R.sup.1 R.sup.2 C.dbd.CH--CH.sub.2 --CO--O--R.sup.3 (I, where R.sup.1 is an organic radical, R.sup.2 is H or R.sup.1, or R.sup.1 and R.sup.2 together form a 5-membered to 20-membered ring, and R.sup.3 is H or lower alkyl) are prepared by carbonylation of R.sup.1 R.sup.2 C(OH)--CH.dbd.CH.sub.2 (II) in the presence of an alcohol R.sup.3' --OH (III, where R.sup.3' is lower alkyl) or, for the preparation of the acids I alone, in the absence of an alcohol III, at from 50.degree. to 150.degree. C. and under from 200 to 700 bar, using a complex of a palladium halide and a tertiary organic phosphine.Type: GrantFiled: December 11, 1984Date of Patent: April 29, 1986Assignee: BASF AktiengesellschaftInventors: Walter Himmele, Werner Hoffmann, Lothar Janitschke
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Patent number: 4540811Abstract: A carboxylic acid esters, such as methyl propionate, is prepared by carbonylation of an olefin, such as ethylene, in the presence of an alcohol by the use of a molybdenum-nickel-alkali metal, a tungsten-nickel-alkali metal or a chromium nickel-alkali metal co-catalyst and in the presence of a halide.Type: GrantFiled: September 30, 1982Date of Patent: September 10, 1985Assignee: The Halcon SD Group, Inc.Inventor: Nabil Rizkalla
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Patent number: 4539424Abstract: Linear esters, e.g., alkyl adipates, are facilely prepared by reacting an alcohol and carbon monoxide with a monoolefin, in the presence of cobalt, optionally hydrogen, and a tertiary nitrogen base, and in a reaction solvent which comprises a 5- or 6-membered monoheterocycle containing from 1 to 3 identical or different, non-adjacent oxygen and divalent sulfur heteroatoms, with the proviso that such heterocycle can also contain from one to two carbon-carbon double bonds, and, if a 5-membered heterocycle, can also contain a nitrogen heteroatom separated from an oxygen or sulfur heteroatom by at least one ring carbon atom and linked to one of the adjacent carbon atoms by a double bond.Type: GrantFiled: October 19, 1983Date of Patent: September 3, 1985Assignee: Rhone-Poulenc Chimie de BaseInventor: Jean Jenck
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Patent number: 4523027Abstract: Carboxylates which contain aldehydes, acetals and/or unsaturated compounds and are obtained by reacting an olefinically unsaturated compound with carbon monoxide and an alkanol are purified by a process wherein the said carboxylates are treated with hydrogen at elevated temperatures in the presence of an acidic ion exchanger or zeolite doped with one or more metals of group VIII of the periodic table, and the resulting low and/or high boilers are separated off by distillation.Type: GrantFiled: July 28, 1983Date of Patent: June 11, 1985Assignee: BASF AktiengesellschaftInventors: Rudolf Kummer, Heinz-Walter Schneider, Volker Taglieber, Franz-Josef Weiss
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Patent number: 4501917Abstract: The invention relates to a process for reacting RO--CH.sub.2 --OR formaldehyde acetals with carbon monoxide in the liquid phase on an acid organic ion exchange material as catalyst. The main products are ether-esters, RO--CH.sub.2 --COOR, of hydroxyacetic acid (glycolic acid).Type: GrantFiled: August 5, 1982Date of Patent: February 26, 1985Assignee: Hoechst AktiengesellschaftInventors: Hans-Joachim Schmidt, Hans-Jurgen Arpe
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Patent number: 4482497Abstract: A carboxylic acid, such as acetic acid, is prepared by carbonylation of a hydrocarbyl alcohol, such as methanol by the use of a molybdenum-nickel-alkali metal or a tungsten-nickel-alkali metal co-catalyst in the presence of an iodide or bromide.Type: GrantFiled: September 30, 1982Date of Patent: November 13, 1984Assignee: The Halcon SD Group, Inc.Inventor: Nabil Rizkalla
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Patent number: 4480121Abstract: The invention is a process for preparing a 2-halo-1-alkene comprising contacting a hydrocarbon stream with a hydrogen halide, in the presence of water and an effective amount of a catalyst, at a temperature between about 20.degree. C. and about 400.degree. C., wherein; the hydrocarbon stream comprises a 1,2-diene, a terminal acetylene or mixtures thereof, represented by the formulas CH.sub.2 .dbd.C.dbd.CH--R or CH.tbd.C--CH.sub.2 --R wherein R is hydrogen, alkyl, cycloalkyl or aryl and may be substituted or unsubstituted; the water is present in an amount capable of maintaining the selectivity of the catalyst for the insertion of the halide on the 2 carbon of the 1,2-diene or terminal acetylene; and the catalyst comprises carbon, silica alumina, aluminosilicates, silica gel, silica, silica magnesia, silicalite, group IIIA, IIIB, IVA, IVB or V metal oxides or rare earth oxides.Type: GrantFiled: August 26, 1982Date of Patent: October 30, 1984Assignee: The Dow Chemical CompanyInventors: Robert T. Klun, Craig B. Murchison, Dennis A. Hucul
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Patent number: 4454333Abstract: Esters of .beta.,.gamma.-unsaturated carboxylic acids are prepared by (i) carbonylating a conjugated diene with carbon monoxide in the presence of an alcohol, a halogenated hydracid and a palladium catalyst; (ii) distilling the carbonylation reaction product in the presence of an ammonium, phosphonium or arsonium quaternary onium chloride or bromide having a melting point below the temperature at which the carbonylation reaction is carried out, and at a temperature and pressure such that said reaction product separates into a gaseous phase and a homogeneous liquid phase; (iii) recovering said gaseous phase comprising the ester of the .beta.,.gamma.Type: GrantFiled: July 23, 1982Date of Patent: June 12, 1984Assignee: Rhone-Poulenc Chimie de BaseInventor: Jean Jenck
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Patent number: 4451667Abstract: This invention is a process for the preparation of acrylate esters comprising contacting a vinyl halide with carbon monoxide and an organic carbonate in the presence of an effective amount of a group VIII metal catalyst.Type: GrantFiled: August 26, 1982Date of Patent: May 29, 1984Assignee: The Dow Chemical CompanyInventors: Robert T. Klun, Thomas W. Regulski
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Patent number: 4450285Abstract: .beta.,.gamma.-Unsaturated esters are prepared by the reaction of the corresponding .beta.,.gamma.-unsaturated carbonate with carbon monoxide in the presence of a group VIII metal catalyst.Type: GrantFiled: February 22, 1982Date of Patent: May 22, 1984Assignee: The Dow Chemical CompanyInventors: Edmund P. Woo, Daniel J. Murray
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Patent number: 4435575Abstract: A process is herein described for preparing carboxylated organic compounds (acids, esters, alkaline salts) of formula ##STR1## wherein R is a hydrocarbyl group having up to 11 carbon atoms (an aliphatic, alicyclic, aryl- or heteroarylalkyl group), also substituted, in its turn, by groups inert under the reaction conditions (alkyl, aryl, etheric, thioetheric, halogen, nitrile, ester, amide, ketonic groups), and R' is a hydrogen atom or an alkyl C.sub.1 -C.sub.8 group, by reaction of carbon monoxide with the corresponding hydrocarbyl halides, having the halogen bound to a non-tertiary carbon atom, in the presence of catalysts which are salts of cobalt hydrocarbonyl, or precursors thereof, in a hydro-alcoholic or alcoholic solvent and in the presence of bases.The process is characterized in that the catalytic system composed by the salt of cobalt hydrocarbonyl is supported on an anion exchange resin.Type: GrantFiled: June 30, 1981Date of Patent: March 6, 1984Assignee: Montedison S.p.A.Inventors: Gianfranco Cainelli, Marco Foa', Achille U. Ronchi, Andrea Gardano
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Patent number: 4433164Abstract: Esters of .beta.,.gamma.-unsaturated carboxylic acids, e.g., penten-3-oates, are prepared by carbonylating a necessarily conjugated diene, e.g., butadiene, with carbon monoxide, in the presence of (i) an alcohol corresponding to the desired ester, (ii) a halogen hydracid, (iii) a palladium catalyst which comprises palladium metal, a palladium oxide, or a salt of palladium, or ionic complex thereof, the anion coordinated with the palladium cation of which being a hard or intermediate base, and (iv) a quaternary onium salt of elemental nitrogen, phosphorus or arsenic, said elemental nitrogen, phosphorus or arsenic being tetracoordinated with carbon atoms and the anion of said salt comprising a hard or intermediate base.Type: GrantFiled: January 20, 1982Date of Patent: February 21, 1984Assignee: Rhone-Poulenc IndustriesInventor: Jean Jenck
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Patent number: 4433165Abstract: The present invention provides for an improved process wherein an olefin, an alcohol, or an ester, halide or ether derivative of said alcohol is reacted with carbon monoxide in a liquid phase in the presence of a catalyst system that contains (a) a rhodium component, and (b) an iodine or bromine component. By passing at least a portion of the liquid reaction mass from the reaction zone to a separation zone of substantially lower CO partial pressure, at least a portion of the carbonylation products, as well as unreacted carbon monoxide, inert gases, and unreacted olefin, alcohol, or alcohol derivatives are vaporized and can be withdrawn from the separation zone. Precipitation of the rhodium catalyst under carbon monoxide deficient conditions is prevented or retarded by addition to the system of a stabilizer component selected from N,N,N',N'-tetramethyl-o-phenylenediamine and 2,3'-dipyridyl.Type: GrantFiled: December 29, 1980Date of Patent: February 21, 1984Assignee: Monsanto CompanyInventor: Thomas C. Singleton
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Patent number: 4433166Abstract: The present invention provides for an improved process wherein an olefin, an alcohol, or an ester, halide or ether derivative of said alcohol is reacted with carbon monoxide in a liquid phase in the presence of a catalyst system containing a rhodium component and an iodine or bromine component. By passing at least a portion of the liquid reaction mass from the reaction zone to a separation zone of substantially lower CO partial pressure, at least a portion of the carbonylation products, as well as unreacted carbon monoxide, inert gases, and unreacted olefin, alcohol, or alcohol derivatives are vaporized and can be withdrawn from the separation zone. Precipitation of the rhodium catalyst under carbon monoxide deficient conditions is prevented or retarded by addition to the system of a stabilizer which is a tin component which may be tin or a tin compound.Type: GrantFiled: December 29, 1980Date of Patent: February 21, 1984Assignee: Monsanto CompanyInventors: Thomas C. Singleton, Frank E. Paulik
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Patent number: 4414409Abstract: Carbonylation of olefins is carried out in the presence of a hydroxylic compound, carbon monoxide and a catalyst system comprising an organic phosphine liganded palladium compound and a perfluorosulfonic acid.Type: GrantFiled: December 21, 1981Date of Patent: November 8, 1983Assignee: E. I. Du Pont de Nemours & CompanyInventor: Francis J. Waller
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Patent number: 4390717Abstract: A process for preparing a carboxylic acid ester of a dicyclopentadiene by reacting the dicyclopentadiene with carbon monoxide and an alcohol in the presence of a cobalt compound catalyst, characterized by carrying out said reaction in the presence of 0.5 mole or more of a pyridine base per mole of the dicyclopentadiene at a temperature of 130.degree. C. or less at a carbon monoxide pressure of preferably at least 20 kg/cm.sup.2. G to hydroesterify the double bond in the norbornene ring, thereby forming a mono-carboxylate of a dicyclopentadiene, and hydroesterifying the monoesterification product as produced or the isolated monoester to the same reaction conditions as above except that the temperature is 160.degree. C. or less to hydroesterify the remaining double bond of the monoester, thereby forming a dicarboxylate of dicyclopentadiene.Type: GrantFiled: April 24, 1981Date of Patent: June 28, 1983Assignee: Japan Synthetic Rubber Co., Ltd.Inventors: Katuhiro Ishikawa, Ryotaro Ohno, Masatoshi Arakawa
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Patent number: 4364869Abstract: A process for the production of alkyl esters of saturated aliphatic carboxylic acids by reacting in an alkoxycarbonylation stage olefins with carbon monoxide and alkanol in the presence of a catalyst consisting of a cobalt compound and a promoter from the group of pyridine, non-ortho-substituted alkylpyridine or mixtures thereof at elevated pressure and elevated temperature. The reaction mixture produced is reprocessed and the pyridine, non-ortho-substituted alkylpyridine, or mixture used as the promoter is rectified prior to its feedback into the alkoxycarbonylation stage in the presence of a given carboxylic acid which is thermally stable under the conditions of reprocessing and which forms a maximum azeotrope with the promoter under the conditions of rectification.Type: GrantFiled: July 29, 1981Date of Patent: December 21, 1982Assignee: Chemische Werke Huls A.G.Inventors: Wolfgang H. E. Muller, Peter Hofmann
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Patent number: 4354036Abstract: A carboxylic acid ester, such as methyl propionate, is prepared by carbonylation of an olefin, such as ethylene in the presence of an alcohol by the use of a molybdenum-nickel or tungsten-nickel co-catalyst in the presence of a promoter comprising an organo-phosphorus compound or an organo-nitrogen compound wherein the phosphorus and nitrogen are trivalent and in the presence of a halide.Type: GrantFiled: May 28, 1981Date of Patent: October 12, 1982Assignee: The Halcon SD Group, Inc.Inventor: Nabil Rizkalla
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Patent number: 4336399Abstract: A process for producing a carboxylic acid and/or its ester, which comprises reacting an alcohol or ether with carbon monoxide in the presence of elemental nickel or a nickel compound, iodine or an iodine compound and an organic compound of a trivalent nitrogen-group element; wherein the iodine or iodine compound is selected from the following formulae (I) to (IV),RX.sub.n (I)wherein R represents a hydrogen atom or an alkyl or alkylene group, X represents an iodine or bromine atom, and n is an integer of 1 to 3, at least one of n.multidot.X's being an iodine atom,I.sub.2 or I.sub.3 - (II)RCOI (III)wherein R represents an alkyl group,MI.sub.2 (IV)wherein M represents an alkaline earth metal, and the amount of the iodine or iodine compound is such that the amount of the free iodine or iodine compound not chemically bonded to the nickel or nickel compound or the organic compound of a nitrogen-group element is at least 0.Type: GrantFiled: November 10, 1980Date of Patent: June 22, 1982Assignee: Mitsubishi Gas Chemical Company, Inc.Inventors: Tomiya Isshiki, Yasuhiko Kijima, Yuh Miyauchi
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Patent number: 4290905Abstract: An ester compound having the formula ##STR1## where R represents a normal alkyl group having one to eight carbon atoms. A method of synthesizing the compounds is presented. The compounds have relatively low melting points, and are particularly useful in combination with other liquid crystal compounds.Type: GrantFiled: December 26, 1979Date of Patent: September 22, 1981Assignee: Kabushiki Kaisha Suwa SeikoshaInventor: Sadao Kanbe
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Patent number: 4263443Abstract: Hydrocarbons and esters and/or acids are produced by heating aldehydes in the presence of an alcohol or an alcohol equivalent and in the presence of an iodine or bromine moiety and a rhodium or iridium catalyst.Type: GrantFiled: November 22, 1978Date of Patent: April 21, 1981Assignee: Halcon Research and Development Corp.Inventor: John F. White
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Patent number: 4257973Abstract: Water, primary alcohols or secondary alcohols together with carbon monoxide can be added across ethylenic or acetylenic bonds in a wide variety of organic compounds to form acids or esters. The reaction is conducted in the presence of a catalyst system consisting of an organophosphorus palladium halide compound and certain metal halide compounds.Type: GrantFiled: November 5, 1971Date of Patent: March 24, 1981Assignee: E. I. Du Pont de Nemours and CompanyInventor: Joseph J. Mrowca
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Patent number: 4255591Abstract: 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: GrantFiled: November 20, 1978Date of Patent: March 10, 1981Assignee: Monsanto CompanyInventors: Earle C. Makin, Jerry L. Price, Yu W. Wei
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Patent number: 4234740Abstract: A process for preparing a diester of a dicarboxylic acid having two more carbon atoms than the unsaturated hydrocarbon used as the starting material, which comprises subjecting an unsaturated hydrocarbon, carbon monoxide and an alcohol to reaction in the presence of a platinum group metal or a salt thereof; a compound selected from the group consisting of nitric acid, a nitrogen oxide and an ester of nitrous acid; and a halogen compound.Type: GrantFiled: November 28, 1978Date of Patent: November 18, 1980Assignee: Ube Industries, Ltd.Inventors: Sumio Umemura, Kanenobu Matsui, Yoshinari Ikeda, Katsuro Masunaga, Takumi Kadota
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Patent number: 4212989Abstract: In a process for producing a carboxylic acid or its ester by reacting an alcohol or an ether with carbon monoxide, the improvement wherein the reaction is performed in the presence of, as a solvent, an aryl ester of an aliphatic carboxylic acid represented by the formula ##STR1## wherein n is an integer of 1 to 5, R.sub.1 represents hydrogen or C.sub.1 -C.sub.4 alkyl or alkenyl, and R.sub.2 represents hydrogen, alkyl, aryl, alkenyl, hydroxymethyl, acyl, acyloxy, formyl, carboxy, hydroxy, halogen, sulfo, nitro, nitroso, amino, acid amide or cyano, and two or more R.sub.2 groups may be the same or different, and the substituents R.sub.2 may be bonded to each other to form a penta- or hexa-carbocyclic or heterocyclic ring.Type: GrantFiled: October 26, 1978Date of Patent: July 15, 1980Assignee: Mitsubishi Gas Chemical Company, Inc.Inventors: Tomiya Isshiki, Yasuhiko Kijima, Yuh Miyauchi