Abstract: A process for the carbonylation of a carbonylatable reactant having a carbonylatable moiety having at least two carbon atoms and/or a reactive derivative thereof which process comprises contacting said carbonylatable reactant and/or a reactive derivative thereof with carbon monoxide in a liquid reaction composition in a carbonylation reactor characterized in that the liquid reaction composition comprises: (a) an iridium catalyst, (b) a halide, (c) at least a finite concentration of water, (d) a carbonylatable reactant having a carbonylatable moiety having at least two carbon atoms and/or a reactive derivative thereof and (e) as promoter, at least one of ruthenium and osmium.

Abstract: Catalysts of the formula I?A.sub.a B.sub.b O.sub.x !.sub.p ?C.sub.c D.sub.d Fe.sub.e Co.sub.f E.sub.i F.sub.j O.sub.y !.sub.q I,whereA is bismuth, tellurium, antimony, tin and/or copper,B is molybdenum and/or tungsten,C is an alkali metal, thallium and/or samarium,D is an alkaline earth metal, nickel, copper, cobalt, manganese, zinc, tin, cerium, chromium, cadmium, molybdenum, bismuth and/or mercury,E is phosphorus, arsenic, boron and/or antimony,F is a rare-earth metal, vanadium and/or uranium,a is from 0.01 to 8,b is from 0.1 to 30,c is from 0 to 4,d is from 0 to 20,e is from 0 to 20,f is from 0 to 20,i is from 0 to 6,j is from 0 to 15,x and y are numbers determined by the valency and frequency of the elements other than oxygen in I, and p and q are numbers whose ratio p/q is in the range from 0.001 to 0.

Abstract: A process for preparing polymeric amides is disclosed. The process comprises sequentially reacting a hydrocarbon polymer functionalized (e.g., via the Koch reaction) to contain acid, ester, thioacid and/or thioester groups with a heavy polyamine to form a partially derivatized product in which at least about 85% of the functional groups are converted to heavy (thio)amide groups, and then reacting the partially derivatized product with an excess of light amine to complete the derivatization by converting substantially all of the remaining functional groups to light (thio)amide groups. Products of the foregoing process are also disclosed, which products are useful as additives in fuels and in lubricants.

Abstract: Pentenoic acids are selectively prepared via hydroxycarbonylation of butadiene with carbon monoxide and water, at a temperature above 30.degree. C., under a partial pressure of carbon monoxide, measured at 25.degree. C., equal to or greater than 0.5 bar, in the presence of a catalytically effective amount of an iridium-based catalyst and an iodine-containing or bromine-containing promoter therefor, in a solvent medium, wherein the iodine or bromine/iridium molar ratio is less than or equal to 20/1 and the concentration by weight of water in the reaction mixture is less than or equal to 8%.

Abstract: The invention provides a process for the carbonylation of an olefinically or acetylenically unsaturated compound which comprises:(a) reacting the unsaturated compound with carbon monoxide and a co-reactant in the presence of a carbonylation catalyst, obtainable by combining a source of platinum group metal cations, a phosphine ligand and an anion, to produce a reaction mixture comprising a carbonylation product, the carbonylation catalyst, and excess of the olefinically or acetylenically unsaturated compound and/or the co-reactant, and(b) recovering the carbonylation product by distillation of the reaction mixturewherein a catalytically active concentrate is removed from the reaction mixture prior to step (b).

Abstract: The process for carbonylating olefins with carbon monoxide in the presence of water, an alcohol or a carboxylic acid and a halogen-free catalyst comprises using a catalyst comprising nickel or a nickel compound and at least one of the metals of the group consisting of chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver and gold, or a compound of these metals.

Abstract: A process for the carbonylation of butadiene or a butadiene derivative in the presence of (i) carbon monoxide, (ii) an alcohol or water, and (iii) a catalyst system comprising palladium, a carboxylic acid and a monodentate phosphine ligand. The amounts of reactants during the carbonylation process are controlled so that the molar ratio of butadiene or butadiene derivative to palladium in the reaction mixture is less than about 70:1, the molar ratio of carboxylic acid to palladium is greater than about 10:1 and the molar ratio of alcohol or water to butadiene or butadiene derivative is less than about 2:1.2. Good selectivity and conversions are advantageously achieved.

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.

Abstract: A process is provided for carbonylation of ethylenic unsaturation comprising the steps of: providing a catalyst system comprising a) a Group VIII metal compound, b) an organic phosphine, and c) and acid; and contacting acetylene, the catalyst system, carbon monoxide, hydrogen, and a nucleophilic compound under conditions effective to carbonylate the acetylene. The presents of hydrogen unexpectedly improves the yield of the desired product (i.e., acrylic acid or the ester thereof).

Abstract: Butadiene or derivative thereof is selectively hydroxycarbonylated into at least one pentenoic acid (the pentenoic acids are themselves facilely converted, via hydroxycarbonylation, into adipic acid, a basic starting material for the production of nylon 66 polymers), by reacting same with carbon monoxide and water, at a pressure greater than atmospheric, in the presence of a catalytically effective amount of (1) a palladium catalyst which is soluble in the medium of reaction and (2) crotyl chloride, the amount of the crotyl chloride being at least two mol thereof per mole of palladium values and said palladium values/crotyl chloride at least in part comprising a palladium/crotyl pi-complex, and the amount of water present in the medium of reaction being no greater than about 20% by weight thereof.

Abstract: In the production step, alcohol is reacted with carbon monoxide in a reaction solvent in the presence of a rhodium-containing solid catalyst obtained by immobilizing rhodium in an insoluble carrier (I) containing a pyridine ring in its resin structure and an alkyl iodide containing an alkyl group of 1 to 5 carbon atoms, to produce a reaction product having a water content of 0.5 to 10% by weight; and in the subsequent removing step, an organic carboxylic acid is separated and recovered from the reaction product, and the recovered organic carboxylic acid is contacted with an insoluble carrier (II) containing a pyridine ring in its resin structure, to remove an iodide contained in the organic carboxylic acid.

Abstract: A process for the production of a carboxylic acid by carbonylation of an alkyl alcohol or its reactive derivative comprises contacting the reactant with carbon monoxide in a liquid reaction composition comprising: (a) an iridium catalyst or rhodium catalyst, (b) alkyl halide, (c) at least a finite concentration of water and (d) rhenium as promoter.

Abstract: A carbonylation catalyst useful for the carbonylation of methanol to acetic acid, acetic anhydride or both comprises a polymer support containing pendant pyrrolidone groups which support a rhodium species. Other polymeric supports capable of withstanding carbonylation temperatures of at least 150.degree. C. are disclosed for the carbonylation reaction in which rhodium levels in the reaction medium of greater than 500 ppm are contemplated.

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.

Abstract: Adipic acid is selectivity prepared by reacting water and carbon monoxide with at least one pentenic acid, in the presence of a catalytically effective amount of an iridium-based catalyst and at least one iodinated promoter therefor at an elevated temperature, at a pressure greater than atmospheric and in at least one solvent medium which comprises a saturated aliphatic or cycloaliphatic hydrocarbon or halogenated derivative thereof, an aromatic hydrocarbon or halogenated derivative thereof, or an aliphatic, aromatic or mixed ether, and wherein the I/Ir atomic ratio is less than 20.

Abstract: In a process for preparing methyltris(m-sulfonatophenyl)phosphonium iodide trisodium salt, the sodium salt of trisulfonated triphenylphosphine and methanol are introduced as the initial charge, a solution of methyl iodide in methanol is added dropwise at elevated temperature, and after an additional reaction time the reaction product is evaporated to dryness in vacuo.Methyltris(m-sulfonatophenyl)phosphonium iodide trisodium salt can be used to prepare carboxylic acids and/or their esters by carbonylation of saturated aliphatic alcohols having from 1 to 20 carbon atoms or their halo, ester or ether derivatives over a rhodium catalyst in the presence of water and methyl iodide under a CO partial pressure of from 0.3 to 200 bar at a temperature of from 100.degree. to 240.degree. C., provided methyltris(m-sulfonatophenyl)phosphonium iodide trisodium salt and carboxylic acid are added to the liquid phase prior to carbonylation.

Abstract: A methanol carbonylation catalyst includes a rhodium complex supported on a porous, cross-linked vinylpyridine resin, wherein the vinylpyridine resin has a cross-linking degree of 30-60%, a pore volume of 0.1-0.4 ml/g and an average pore diameter of 20-100 nm. The catalyst may be prepared by contacting the pyridine ring-containing resin with an aqueous solution containing rhodium ion and then contacting the resulting rhodium ion-carrying resin with carbon monoxide and an alkyl iodide in an organic solvent to convert the rhodium ion to a rhodium complex bound to the resin. Acetic acid is produced by reacting carbon monoxide with methanol at a temperature of 140.degree.-250.degree. C. and a partial pressure of carbon monoxide of 7-30 kg/cm.sup.2 in the presence of an alkyl iodide and the above catalyst.

Abstract: 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.

Abstract: Conversion of certain lactones by reaction with carbon monoxide and water, in the presence of a homogeneous rhodium catalyst and an iodide or bromide promoter, to produce adipic acid.

Abstract: Adipic acid is selectively prepared via hydrocarboxylation of pentenoic acids, by reacting water and carbon monoxide with at least one pentenoic acid, in the presence of a catalytically effective amount of a rhodium-based catalyst and at least one iodinated promoter therefor, at a temperature ranging from 100.degree. to 240.degree. C. and a pressure greater than atmospheric, and wherein (a) such reaction is carried out in the absence of a third reaction solvent and (b) the carbon monoxide partial pressure, measured at 25.degree. C., is less than or equal to 20 bar.

Abstract: The invention relates to a direct process for the preparation of alkanedioic derivatives, for example alkanedioic diesters, by reaction of an aliphatic conjugated diene such as butadiene with carbon monoxide and a hydroxyl group-containing compound such as a C.sub.1-6 alkanol in the presence of a catalyst system containinga) a source of cationic palladium,b) a first bidentate diphosphine ligand having electron-withdrawing substituents on the phosphorus atoms,c) a second bidentate diphosphine ligand having electron-releasing substituents on the phosphorus atoms, andd) a source of an anion.

Abstract: Six carbon diacids or lactones or 5 carbon lactones or 6 carbon diacid anhydrides or branched mono-olefinic five carbon acids are converted (isomerized) to adipic acid or pentenoic acids by reacting them is the presence of carbon monoxide and a iodide promoted iridium catalyst.

Abstract: Lower carboxylic acids such as acetic acid, are produced efficiently from inexpensive lower alkanes such as methane by allowing the lower alkanes to react with carbon monoxide in the presence of palladium and/or copper catalysts and salts of peroxy acids.

Abstract: The invention relates to a catalyst system, which comprises a source of a Group VIII metal and a polyphosphine. The invention further relates to a process for the preparation of alpha, beta-olefinically unsaturated compounds utilizing this catalyst system.

Abstract: Preparation of 3-pentenoic acid by reacting butadiene and carbon monoxide using a rhodium catalyst and a sulfonic acid catalyst in water and a carboxylic acid solvent.

Abstract: Adipic acid is selectively prepared by reacting water and carbon monoxide with at least one pentenic acid, in the presence of an iridium-based catalyst and at least one iodine-containing promoter therefor, at an elevated temperature, at a pressure greater than atmospheric pressure, in a reaction medium comprising at least one saturated aliphatic carboxylic acid, ethylenically unsaturated aliphatic carboxylic acid or aromatic carboxylic acid having not more than 20 carbon atoms, with the I/Ir atomic ratio being less than 10.

Abstract: Adipic acid is selectively prepared, in good yields, by reacting at least one pentenic acid with water and carbon monoxide, the partial pressure of which, measured at 25.degree. C., being less than or equal to 12 bar, in the presence of a catalytically effective amount of a rhodium-based catalyst and at least one iodine-containing promoter therefor, at a temperature ranging from 100.degree. to 240.degree. C. and at superatmospheric pressure, and in a liquid reaction medium which comprises at least one hydrocarbon or chlorocarbon solvent, whether a saturated aliphatic or cycloaliphatic hydrocarbon, aromatic hydrocarbon or chlorinated derivative thereof.

Abstract: A process for the preparation of adipic acid from pentenoic compounds by hydrocarboxylation using an iridium catalyst, an iodide promoter, water, carbon monoxide and a carboxylic acid solvent.

Abstract: Adipic acid is selectively prepared, in good yields, by reacting at least one pentenic acid with water and carbon monoxide, the partial pressure of which, measured at 25.degree. C., being less than or equal to 20 bar, in the presence of a catalytically effective amount of a rhodium-based catalyst and at least one iodine-containing promoter therefor, at a temperature ranging from 100.degree. to 240.degree. C. and at superatmospheric pressure, and in a liquid reaction medium which comprises a saturated aliphatic or aromatic carboxylic acid having up to 20 carbon atoms.

Abstract: A process for the preparation of an alpha,beta-olefinically unsaturated compound, which comprises reacting an acetylenically unsaturated compound with monoxide and a hydroxyl-containing compound in the presence of a catalyst system comprising:(a) a source of a Group VIII metal cation,(b) a source of an organic diphosphine having at least one of the phosphorus atoms substituted by an aromatic substituent containing an imino nitrogen atom, and(c) a source of an anion.

Abstract: A process for the manufacture of adipic acid by reacting 1,3-butadiene or an allylic butenol or the like with carbon monoxide and water using a rhodium catalyst and an HI or HBr promoter, removing adipic acid from the reaction mixture, and reacting at least part of the remaining portion of the reaction mixture to form additional adipic acid.

Abstract: 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.

Abstract: Preparation of 3-pentenoic acid from butadiene, water and carbon monoxide in an organic acid solvent in the presence of a rhodium catalyst and a bromide or iodide promoter.

Abstract: A process for the preparation of an alkyl methacrylate, which process comprises:a) selectively removing propadiene from a C.sub.3 -mixture comprising a mixture of propyne and propadiene that has been obtained from an ethene cracker, a catalytic cracker or an LPG-dehydrogenation process, to provide a propyne feed in which the ratio of propyne to propadiene is at least about 6:1, ndb) contacting the propyene feed with carbon monoxide and an alkanol in the presence of a carboxylation catalyst.

Abstract: A process for the hydrocarboxylation of alkenes and non-conjugated olefinically unsaturated nitriles and esters using a rhodium catalyst, a bromide or iodide promoter, and a nitrile accelerator.

Abstract: .beta.,.gamma.-Unsaturated carboxylic acids are facilely prepared by carbonylating a conjugated diene with carbon monoxide in the presence of (i) water, (ii) a halogenated hydracid, (iii) a palladium catalyst comprising palladium metal or supported palladium metal, a palladium oxide, or a complex salt of palladium, the anion coordinated to the palladium cation of which comprising a hard or borderline base, and (iv) a quaternary onium salt of nitrogen, phosphorus or arsenic, said N, P or As being tetra-coordinated to a carbon atom, the anion of which comprising a hard or borderline base.

Abstract: A process for the selective carbonylation of a conjugated diene by contacting with carbon monoxide in the presence of a hydroxyl-group-containing compound such as water, alcohol, phenol or carboxylic acid in liquid phase using a catalyst system formed by the combination of:(a) a palladium compound and(b) at least one organic bidentate phosphine.

Abstract: A catalyst system which comprises:a) a group VIII metal compound, andb) a monophosphine of formula ##STR1## where R.sup.1 represents an aliphatic hydrocarbyl group, R.sup.2 represents an optionally substituted aromatic heterocyclic group having 5 or 6 ring atoms of which at least one is nitrogen, which may form part of an optionally substituted larger condensed ring structure, and R.sup.3 independently has the meaning of R.sup.2 or represents an optionally substituted aryl group or an acid addition salt thereof, and their use in the carbonylation of unsaturated compounds.

Abstract: 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.

Abstract: A method for the preparation of alpha,beta-olefinic unsaturated compounds by means of carbonylation of acetylenic unsaturated compounds with carbon monoxide in the presence of a hydroxy-containing compound in liquid phase, accomplished in the presence of a catalytic system that can be formed from:(a) a palladium compound,(b) a protonic acid, and(c) an organic phosphine according to the formula: ##STR1## wherein R.sub.1 represents a heterocyclic five- or six-atom ring, comprising, at least as hetero atom, nitrogen, which may be optionally substituted and/or may form part of a larger condensed ring structure that may be optionally substituted, and wherein R.sub.2 and R.sub.3 each have the aforesaid meaning of R.sub.1 or may represent an optionally substituted aryl group.The invention further comprises novel organic phosphines and compositions containing said phosphines as wel as the catalytic systems containing said phosphines.

Abstract: A process for the preparation of carboxylic acids or of esters thereof by contacting an olefinically unsaturated compound with CO in the presence of water or an alcohol, respectively, and of a catalytic system prepared by combining a ruthenium compound and a compound having a non-coordinating anion of an acid with a pK.sub.a below 0.5; compositions comprising a ruthenium compound and a salt having a non-coordinating anion of an acid with a pK.sub.a below 0.5 are novel.

Abstract: A process is disclosed for producing N-acetyl-aminoacid which comprises reacting a feedstock from the group consisting of simple olefins, acetamide and synthesis gas with a catalyst comprising a cobalt-containing compound promoted by a bidental-phosphine ligand in a solvent at a pressure of 500 psi or greater and a temperature of 50.degree. C. or greater. The presence of the ligand increases both reaction rate and cobalt catalyst stability.

Abstract: Process for preparing adipic acid or esters thereof by:(1) reacting 1,3-butadiene with CO and water or an alcohol with formation of pentenoic acid or esters thereof in the presence of a first carbonylation catalyst comprising a Pd compound and a polydentate ligand containing P, As or Sb,(2) isolating pentenoic acid or esters thereof from the reaction mixture, and(3) reacting the isolated pentenoic acid or esters with CO and water or an alcohol in the presence of a second carbonylation catalyst.

Abstract: A catalyst system for the selective carbonylation of conjugated dienes in the presence of a hydroxyl-group-containing compound in the liquid phase comprising a combination of:(a) palladium or a compound of;(b) an organic phosphorus, antimony or arsenic derivative according to the formula: ##STR1## wherein R.sub.1 represents an aryl group substituted with at least one electron-attracting group and R.sub.2 and R.sub.3 each represent individually an aryl group or an aryl group substituted with at least one electron-attracting group and R.sub.2 and R.sub.3 each represent individually an aryl group or an aryl group substituted with at least one electron-attracting group and wherein Q represents phosphine, antimony or arsenic; and(c) an acid with a pka from about 2.5 to about 4.0, said acid being a condensed aromatic carboxylic acid or a benzoic acid substituted with at least one electron attracting group selected from the group consisting of (1) halogen, (2) hydroxy, and (3) methoxy.

Abstract: The preparation of linear dicarboxylic acids, e.g., adipic acid, by hydrocarboxylating unsaturated monocarboxylic acids, e.g., 3-pentenoic acid, with carbon monoxide and water in the presence of a rhodium-containing catalyst, an iodide promoter and certain inert halocarbon solvents, e.g., methylene chloride.

Abstract: A process for the production of carboxylic acids by the hydrocarboxylation of olefinically unsaturated alkenes or esters using a rhodium catalyst, an iodide promoter, a solvent selected from the class consisting of methylene chloride, 1,2-dichloroethane, and C.sub.6 to C.sub.9 aromatic solvents, and an accelerator which is an acid having a pKa in the range of 4.2 to 5.2.

Abstract: A process for the selective hydrocarboxylation of propylene to produce predominantly isobutyric acid in the liquid phase is provided. The reaction of propylene, carbon monoxide and water is effected at a temperature of about 10.degree. C. to about 80.degree. C. and at a pressure of about 75 psi to about 1500 psi in the presence of a strong acid and a metal phthalocyanine co-catalyst.

Abstract: 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.

Abstract: A process for the carbonylation of an allenically unsaturated compound with CO in the presence of water, an alcohol and/or a carboxylic acid, which process is carried out in the presence of a catalyst formed by combining:(a) a compound of divalent palladium,(b) at least 15 mol of an organic phosphine per gram atom of divalent palladium, and(c) a protonic acid having a pK.sub.a greater than 1.5 and/or a carboxylic acid having a pK.sub.a not greater than 1.5, both measured at 18.degree. C. in aqueous solution.

Abstract: 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.