Abstract: 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.

Abstract: 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.

Abstract: Acetic acid is prepared by heating methyl formate in the presence of carbon monoxide 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.

Abstract: A process for producing a carboxylic acid which comprises reacting a hydrocarbyl alcohol with carbon monoxide in the presence of a metal catalyst selected from nickel or cobalt, a halide and a specific promoter is disclosed. According to the present invention, formation rate of carboxylic acid is high.

Abstract: C.sub.2 to C.sub.10 monocarboxylic acids are co-produced with formic acid by reacting at an elevated temperature below 250.degree. C. a C.sub.1 to C.sub.9 alkyl formate with carbon monoxide and water in the presence as catalyst of a Group VIII noble metal component and an iodine or bromine-containing promoter, the partial pressure of carbon monoxide being in the range 1 to 300 bar, the concentration of noble metal component being in the range from 100 to 5000 ppm and the atomic ratio of noble metal to iodine or bromine being in the range from 1:50 to 1:1000 and thereafter recovering the co-produced C.sub.2 to C.sub.10 monocarboxylic acid and formic acid. In a preferred embodiment, the alkyl formate is methyl formate and the recovered acids are acetic acid and formic acid.

Abstract: A method for making monocarboxylic acids and esters comprising contacting carbon monoxide and a monohydric alcohol containing 1 to 4 carbon atoms in the presence of a crystalline aluminosilicate zeolite having a silica to alumina ratio at least about 6 and a constraint index within the approximate range of 1 to 12 under a pressure of at least one atmosphere. Also coproduced are hydrocarbons, particularly ethylene and "gasoline".

Abstract: 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.

Abstract: A process is disclosed for preparation of a carboxylic acid RCOOH wherein R represents certain alkyl, cycloalkyl or aralkyl groups, by heating a formic acid ester HCOOR in the presence of carbon monoxide, a soluble rhodium catalyst and an iodide or bromide source, promoted by certain oxygen-containing compounds of phosphorus, arsenic or antimony.

Abstract: The disclosure relates to a process for purifying and recovering a contaminated catalyst solution which is obtained in the carbonylation of methyl acetate and/or dimethylether, the catalyst solution containing carbonyl complexes of noble metals of group VIII of the Periodic System of the elements, quaternary heterocyclic aromatic nitrogen compounds or quaternary organophosphorus compounds as organic promoters, and optionally compounds of carbonyl-yielding common metals as inorganic promoters, undistillable organic contaminants as well as acetic acid, acetic anhydride and ethylidene diacetate.

Abstract: A process is disclosed for the synthesis of alpha-amino acid by first contacting the condensation product of an aldehyde or ketone and an amine or amide with a protic or Lewis acid solvent and carbon monoxide to form an intermediate reaction product, and then hydrolyzing the intermediate to yield a product comprising the alpha-amino acid. The reaction rate and product yield can be increased by the addition of a Group 1B metal oxide catalyst in the first step.

Abstract: A process for homologating alcohols and/or acids to a mixture of higher acids by reaction with syngas in the presence of a ruthenium-rhodium-iodide-titanium(IV) catalyst.

Abstract: Process using selected sulfones, e.g., tetramethylenesulfone as solvents in the carbonylation of nitriles, e.g., 3-pentenenitrile and acids, e.g., 3-pentenoic acid to produce highly linear products.

Abstract: A process for the production of an N-acyl-.alpha.-amino acid represented by the general formula ##STR1## wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4, independently from each other, represent a hydrogen atom, an alkyl or cycloalkyl group which may be substituted, or an aryl or heteroaromatic group selected from the group consisting of furyl, pyrrolyl, pyridinyl, thienyl and indolyl which may be substituted, which comprises reacting an oxirane represented by the general formula ##STR2## wherein R.sup.1 and R.sup.2 are as defined above, an amide compound represented by the general formulaR.sup.3 CONHR.sup.4 (III)wherein R.sup.3 and R.sup.4 are as defined above, and carbon monoxide in the presence of hydrogen, a cobalt-containing catalyst, and a promoter composed of a compound containing a metal selected from Groups I, II, III and IV of the periodic table.

Abstract: 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.

Abstract: A process for the production of .alpha.-keto-carboxylic acids of the general formula: ##STR1## wherein R.sub.1 and R.sub.2 are the same or different and are hydrogen, hydrocarbyl radicals, substituted hydrocarbyl radicals or hydrocarbyloxy radicals by reacting an acyl halide of the formula: ##STR2## wherein R.sub.1 and R.sub.2 are as defined above and X represents halogen, in a liquid solvent medium, with an alkali metal tetracarbonyl cobaltate complex of the formula:MCo(CO).sub.4wherein M is an alkali metal to form the corresponding acylcobaltcarbonyl complex of the formula: ##STR3## wherein R.sub.1 and R.sub.2 are as defined above, reacting the acylcobaltcarbonyl complex thus formed with carbon monoxide and an alkali metal hydroxide or an alkaline earth metal hydroxide at elevated temperature and elevated pressure in a liquid solvent medium to form the corresponding alkali metal salt or alkaline earth metal salt of the product .alpha.-keto-carboxylic acid and thereafter acidifying the salt of the .alpha.

Abstract: A process for the production of .alpha.-keto-carboxylic acids of the general formula: ##STR1## wherein R.sub.1 and R.sub.2 are the same or different and are hydrogen, hydrocarbyl radicals, substituted hydrocarbyl radicals or hydrocarbyloxy radicals by reacting an acyl halide of the formula: ##STR2## wherein R.sub.1 and R.sub.2 are as defined above and X represents halogen, in a liquid solvent medium, with an alkali metal tricarbonyl[triphenylphosphine]cobaltate complex of the formula:MCo(CO).sub.3 Ph.sub.3wherein M is an alkali metal to form the corresponding phenylacetyl tricarbonyl[triphenylphosphine]cobalt complex of the formula: ##STR3## wherein R.sub.1 and R.sub.2 are as defined above, reacting the acylcobaltcarbonyl complex thus formed with carbon monoxide and an alkali metal hydroxide or an alkaline earth metal hydroxide at elevated temperature and elevated pressure in a liquid solvent medium to form the corresponding alkali metal salt or alkaline earth metal salt of the product .alpha.

Abstract: The disclosure relates to a process for purifying and recovering a contaminated catalyst solution which is obtained in the carbonylation of methyl acetate and/or dimethylether, the catalyst solution containing carbonyl complexes of noble metals of group VIII of the Periodic System of the elements, quaternary heterocyclic aromatic nitrogen compounds or quaternary organophosphorus compounds as organic promoters, undistillable organic contaminants as well as acetic acid, acetic anhydride and ethylidene diacetate.

Abstract: Carboxylic acids having the structural formula R.sup.1 COOH, wherein R.sup.1 is a linear, branched or cyclic chain alkyl radical of from 1 to 6 carbon atoms or a phenyl-C.sub.n H.sub.2n -radical wherein 1.ltoreq.n.ltoreq.6, are prepared by carbonylating an alcohol having the formula R.sup.1 -OH with carbon monoxide in liquid phase, in the presence of a catalytically effective amount of nickel and an alkyl or acyl halide promoter therefor, at a temperature of at least about 120.degree. C. and under a total pressure of less than 200 bars, and said carbonylation being carried out in the presence of at least one vanadium compound in which the vanadium is in an oxidation state of 4 or 5, and in an initial carboxylic acid reaction medium having the formula R.sup.2 -COOH, wherein R.sup.2 is defined as was R.sup.1 above, and further wherein R.sup.1 and R.sup.2 may be the same or different.

Abstract: 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.

Abstract: 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.

Abstract: Alkyl carboxylates are hydrocarbonylated and/or carbonylated with carbon monoxide and hydrogen, in an aqueous medium, and in the presence of a catalytically effective amount of a catalyst system comprising (i) ruthenium, (ii) cobalt, (iii) at least one iodine-containing promoter, and (iv) chromium. The subject hydrocarbonylation/carbonylation is admirably well suited, e.g., for the preparation of acetaldehyde, ethanol, ethyl acetate and acetic acid, especially from a methyl carboxylate.

Abstract: Alkyl carboxylates are hydrocarbonylated and/or carbonylated with carbon monoxide and hydrogen, in an aqueous medium, and in the presence of a catalytically effective amount of a catalyst system comprising (i) ruthenium, (ii) cobalt, (iii) at least one iodine-containing promoter, and (iv) vanadium. The subject hydrocarbonylation/carbonylation is admirably well suited, e.g., for the preparation of acetaldehyde, ethanol, ethyl acetate and acetic acid, especially from a methyl carboxylate.

Abstract: Method for the manufacture of ethylidene diacetate by reacting methyl acetate and/or dimethyl ether with carbon monoxide and hydrogen in the presence of a catalyst comprising a Group VIII metal compound and a halogen-containing compound wherein the reaction is carried out in the presence of a sulphur-containing polar solvent.

Abstract: Carboxylic acids having the structural formula R.sup.1 COOH, wherein R.sup.1 is a linear, branched or cyclic chain alkyl radical of from 1 to 6 carbon atoms or a phenyl-C.sub.n H.sub.2n -radical wherein 1.ltoreq.n.ltoreq.6, are prepared by carbonylating an alcohol having the formula R.sup.1 -OH with carbon monoxide in liquid phase, in the presence of a catalytically effective amount of nickel and an alkyl or acyl halide promoter therefor, at a temperature of at least about 120.degree. C. and under a total pressure of less than 200 bars, and said carbonylation being carried out in the presence of at least one lanthanide salt, and in an initial carboxylic acid reaction medium having the formula R.sup.2 -COOH, wherein R.sup.2 is defined as was R.sup.1 above, and further wherein R.sup.1 and R.sup.2 may be the same or different.

Abstract: Alkyl esters, such as ethyl acetate, are prepared by contacting the corresponding next lower carbon number alkyl ester, such as methyl acetate, with carbon monoxide and hydrogen in the presence of an iodine or iodide-free catalyst composition comprising a ruthenium-containing compound, a cobalt containing compound and a quaternary phosphonium salt or base, and heating the mixture to an elevated temperature and pressure for sufficient time to produce the desired higher alkyl ester, and then recovering the same from the reaction mixture.

Abstract: Vinyl esters such as vinyl acetate are hydrocarboxylated with tertiary organo-phosphine stabilized palladium catalysts utilizing low water concentration; the ready hydrolysis of the .alpha.-acetoxypropionic acid affords a convenient route to lactic acid.

Abstract: Process for the carbonylation of alkanols and/or ethers at elevated temperature and pressure in the presence of a Group VIII metal compound and pentachlorobenzenethiol and/or salts thereof, using a pentachlorobenzenethiol compound: Group VIII metal compound molar ratio of not more than 10. The process is of special interest for the production of methyl acetate from methanol using an active, iodine-free catalytic system.

Abstract: Carboxylic acids having the structural formula R.sup.1 COOH, wherein R.sup.1 is a linear, branched or cyclic chain alkyl radical of from 1 to 6 carbon atoms or a .PHI.--C.sub.n H.sub.2n -- radical wherein .PHI. is phenyl and 1.ltoreq.n.ltoreq.6, are prepared by carbonylating an alcohol having the formula R.sup.1 --OH with carbon monoxide in liquid phase, in the presence of a catalytically effective amount of nickel and an alkyl or acyl halide promoter therefor, at a temperature of at least about 120.degree. C. and under a total pressure of less than 200 bars, and said carbonylation being carried out in the presence of at least one chromium salt in which the chromium is in a state of oxidation (p) of greater than zero (p>0), and in an initial carboxylic acid reaction medium having the formula R.sup.2 --COOH, wherein R.sup.2 is defined as was R.sup.1 above, and further wherein R.sup.1 and R.sup.2 may be the same or different.

Abstract: This invention pertains to the production of higher homologues of aliphatic carboxylic acids by reaction of said acids with carbon monoxide and hydrogen in the presence of one or more nickel-containing catalysts in combination with a Group VB tertiary donor ligand and in the presence of an iodide or bromide promoter.

Abstract: This invention pertains to the production of higher homologues of aliphatic carboxylic acids by reaction of said acids with carbon monoxide and hydrogen in the presence of one or more rhodium-containing catalysts and an iodide or bromide promoter.

Abstract: This invention pertains to the production of higher homologues of aliphatic carboxylic acids by reaction of said acids with carbon monoxide and hydrogen in the presence of one or more palladium-containing catalysts in combination with a Group VB tertiary donor ligand and in the presence of an iodide or bromide promoter.

Abstract: Ethylidene diacetate is prepared by treating methyl acetate and/or dimethyl ether with carbon monoxide and hydrogen by the use of a molybdenum-nickel or tungsten-nickel co-catalyst, in the presence of an iodide and 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 an iodide.

Abstract: The invention relates to an improved process for making 1,1-diacetoxyethane by reacting methyl acetate and/or dimethylether with carbon monoxide and hydrogen under practically anhydrous conditions, at temperatures of 350.degree. to 575.degree. K., under pressures of 1 to 300 bars, and in the presence of a catalyst system containing noble metals belonging to group VIII of the periodic system of the elements, or compounds thereof, and iodine and/or its compounds. The improved process is effected in the presence of a catalyst system containing, as additional ingredients, an aliphatic carboxylic acid having 1 to 8 carbon atoms, a heterocyclic aromatic compound, in which at least one hetero atom is a quaternary nitrogen atom, and a manganese or rhenium compound.

Abstract: This invention pertains to the production of higher homologues of aliphatic carboxylic acids by reaction of said acids with carbon monoxide and hydrogen in the presence of one or more ruthenium catalyst components and an iodide or bromide promoter.

Abstract: 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.

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.

Abstract: In the carbonylation of esters and/or ethers the reaction mixture is separated into fractions to recover components therefrom, gases are withdrawn from the system and halogen values are recovered from said gases by contact with a component recovered from said reaction mixture.

Abstract: A process for producing an aliphatic carboxylic acid and an aliphatic carboxylic acid esters ofa phenol which comprises reacting a phenol of the general formula ##STR1## wherein n is an integer of 1 to 6, m is an integer of 0 to 5, the sum of n and m is 6, and R represents hydrogen, alkyl, aryl, alkenyl, carbinol, acyl, acyloxy, formyl, carboxy, halogen, sulfo, nitro, nitroso, amino, amido, or cyano, and two or more R groups may be the same or different, and the substituents R may be bonded to each other to form a penta- or hexa-carboxylic or heterocyclic ring, and an aliphatic carboxylic acid ester or an aliphatic ether with carbon monoxide, and separating and recovering the aliphatic carboxylic acid from the reaction mixture.

Abstract: 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.

Abstract: A process is disclosed for preparing esters having the general formulae:RCOOCH.sub.2 R'andR'COOCH.sub.2 Rwherein R and R' are linear or branched alkyl radicals either like or unlike each other, and containing from 1 to 16 carbon atoms, or considered together, forming a cycloaliphatic ring having up to 7 carbon atoms, wherein carbon monoxide and hydrogen are reacted, at temperatures ranging from 150.degree. to 350.degree. C. and at pressures ranging from 50 to 1000 atmospheres, with an ether of formula R O R' or esters of formula RCOOR' and R'COOR, in which R and R' have the same meanings as specified hereinabove, and in the presence of a catalyst system comprising a ruthenium carbonyl and a promoter selected from the class consisting of hydroiodic acid, carboxylic acid solutions of inorganic or tetraalkylammonium bromides and iodides, and mixtures of these promoters.

Abstract: Vinylacetic acid and optionally .gamma.-butyrolactone are prepared by reacting an allyl compound substituted by oxygen functions with carbon monoxide in the presence of a heavy metal catalyst. When the reaction is carried out with an allyl ether or a carboxylic acid allyl ester, water is added. Vinylacetic acid is obtained in a very good yield in simple and economic manner.