Abstract: Esters are prepared by contacting, under suitable reaction conditions, a feed stream comprising a primary alcohol of 1-4 carbon atoms per molecule (preferably methanol, ethanol) and carbon monoxide with a catalyst composition comprising (a) copper or a copper compound (preferably CuO), (b) zinc oxide, (c) at least one metal or compound of at least one metal selected from the group consisting of cobalt, ruthenium, iridium, platinum, molybdenum, and rhenium (preferably cobalt and/or rhenium) and, optionally, (d) alumina.

Abstract: Organic iodine compounds are separated from carbonylation products of methanol, methyl acetate and dimethyl ether and from mixtures of such carbonylation products by a process wherein the iodine compounds are removed by liquid phase extraction with a non-aromatic hydrocarbon.

Abstract: The invention concerns a method for the preparation of polyoxyalkylene compounds wherein each compound has one primary amine group and one primary hydroxyl group. The method comprises alkoxylating a t-butyl ethylene, propylene or butylene glycol then aminating the product. Finally the t-butyl group is cleaved by an acid. The compounds of the method of this invention are useful in urethane/urea plastics including foams, elastomers and coatings.

Abstract: Allylic 1-hydroxy alcohols are inverted to allylic 3-hydroxy alcohols by: (1) epoxidizing the allyl group of the allylic 1-hydroxy alcohol to the corresponding 2,3-epoxy-1-hydroxy alcohol; (2) transforming the 2,3-epoxy-1-hydroxy alcohol compound to a 1,2-dihalo-3-hydroxy alcohol; and (3) dehalogenating the 1,2-dihalo-3-hydroxy alcohol to form the desired allylic 3-hydroxy alcohol.

Abstract: This invention concerns solid organometallic hydrocarbyloxymagnesium halides of the formula ROMgX wherein RO is a hydrocarbyloxy group of 1 to 20 carbon atoms and X is halide, and a two step process for making these halides comprising:(a) reacting an activated magnesium metal with an alkyl halide of the formula R'X, in which R' is compound containing 1 to 20 carbon atoms, in a dry inert hydrocarbon media, under a dry inert atmosphere to produce a compound of the formula R'MgX in which R' and X have the meanings ascribed to them herein; and,(b) and reacting the R'MgX compound with an oxygen containing compound, containing 1 to 20 carbon atoms, selected from the group consisting of alcohols, ketones, aldehydes and esters to produce the compound ROMgX.When the oxygen containing compound is 2-alkyl substituted, the products are hydrocarbon soluble.

Abstract: A process for producing ethanol which comprises reacting methanol, carbon monoxide and hydrogen in the presence of a catalyst comprising a cobalt phosphine carbonyl complex having the formula:Co(CO).sub.3.R.sub.1 R.sub.2 R.sub.3 P.R.sub.4 R.sub.5 POwherein each of R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 is independently hydrogen, C.sub.1 -C.sub.20 alkyl, C.sub.3 -C.sub.20 cycloalkyl or aryl, and the alkyl, cycloalkyl or aryl may contain a member selected from N, O, S, halogen and mixtures thereof is disclosed.

Abstract: A process for the homologation of an alkanol by reaction with synthesis gas in contact with a system containing rhodium atom, ruthenium atom, iodine atom and a bis(diorganophosphino) alkane to selectivity produce the next higher homologue.

Abstract: A process for producing ethanol which comprises reacting methanol, carbon monoxide and water in the presence of a catalyst comprising cobalt or a cobalt compound and a tertiary phosphine as an effective component is disclosed. A gaseous mixture obtained by burning heavy oil or coal having a relatively high content of carbon can be used as a raw material for producing ethanol.

Abstract: A process for producing ethanol which comprises reacting methanol, carbon noxide and hydrogen in the presence of (a) a catalyst containing a cobalt component, an iron component, a ruthenium component and an iodine component, (b) at least one organic solvent and (c) water, said catalyst comprising the cobalt component in amount of 0.1-500 milligram atom (mg-atom) in terms of cobalt per 1 mol of methanol, an iron component in amount of 0.01-4 atoms per 1 atom of cobalt in terms of metal, a ruthenium component in amount of 0.01-4 atoms per 1 atom of cobalt in terms of metal and an iodine component in amount of 0.05-20 atoms per 1 atom of cobalt is disclosed. According to the present invention, selectivity to ethanol is high and ethanol can be obtained under mild conditions.

Abstract: 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.

Abstract: 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.

Abstract: Internal olefins are rapidly hydroformylated in high selectivity to aldehyde product using homogeneous rhodium catalysts modified with highly sterically hindered tricycloalkyl phosphine ligands under mild process conditions.

Abstract: A process is provided for the hydroformylation of an olefinic compound with carbon monoxide and hydrogen in the presence of cobalt catalyst and a promoter comprised of an organic nitrile. In one aspect, the olefinic compounds are olefinic fatty compounds with at least 4 carbon atoms. In another aspect, the cobalt catalyst consists of only a soluble cobalt salt and a promoter consisting of an organic nitrile such as acetonitrile. In another aspect of the invention, the olefinic compound to be hydroformylated contains a cyano substituent such that the reaction is self promoted.

Abstract: Methanol is converted into alcohols containing at least two carbon atoms by reaction with hydrogen and/or carbon monoxide at elevated temperature and superatmospheric pressure in the presence, as catalyst, of (i) an oxide of Th and/or U and (ii) one or more alkali metals the latter being present in an amount of at least 1% by weight. Preferably the catalyst is free of hydrogenating metals. The methanol can be prepared by reaction of hydrogen and carbon monoxide in the presence of a methanol-forming catalyst.

Abstract: A process for producing ethanol which comprises reacting methanol, carbon monoxide and hydrogen in the presence of (a) a catalyst comprising cobalt or a cobalt compound and a tertiary phosphine as an effective component and (b) promoter comprising an aromatic carboxylic acid, an ester thereof, or a cobalt salt of aromatic carboxylic acid is disclosed. According to the present invention, formation of by-products becomes less and selectivity to realizable ethanol becomes higher.

Abstract: A compound having the general formula R.sub.x COH[COR].sub.y, wherein R is a lower alkyl hydrocarbon radical, y is 0 or 1, and x is 2 when y is 1 and 3 when y is 0, is prepared by admixing carbon monoxide, a transition metal halide, and an organomonolithium compound or an anionic equivalent thereof.

Abstract: A catalyst has been found for the low pressure hydroformylation of alcohols to produce aldehydes. This catalyst consists of a rhodium containing compound, an iodide containing compound, and a chelating Group V compound, which is used alone or in combination with a monodentate, Group V compound.It is the first rhodium-based catalyst that generates acetaldehyde via hydroformylation of the methanol. The reaction is typically carried out at 160.degree.-180.degree. C. and 1000-2000 psi. The acetaldehyde rate and selectivity are 1-5 Mhr.sup.-1 and 50-75%. Conventional cobalt catalysts require operating pressures of at least 3000-6000 psi in order to obtain reasonable productivities.

Abstract: Methods and compositions are provided for asymmetrically donating an oxygen atom to a pair of electrons to produce an asymmetric product. Specifically, a metal alkoxide is used as a catalyst, where the metal has a coordination number of at least four, and at least one, usually two, of the alkoxide groups bonded to the metal are bonded to asymmetric carbon atoms. The metal catalyst is employed in conjunction with a hydroperoxide and an alkanol having a functionality with a pair of electrons capable of accepting an oxygen atom. The resulting product is enriched in one enantiomer due to the enantioselective introduction of an asymmetric center or an enhanced rate of reaction of one of the enantiomers of a chiral alkanol.

Abstract: This invention provides a novel heterogeneous catalyst system adapted for alkanol homologation, which comprises lanthanum hydroxide and a rhodium or ruthenium moiety, e.g. RhCl.sub.3 or RuCl.sub.3.

Abstract: Allyl alcohol is hydroformylated with a gaseous mixture of hydrogen and carbon monoxide, in an aromatic hydrocarbon, in the presence of a rhodium complex and a trisubstituted phosphine, to form hydroxybutyraldehydes which are separated from the reaction mixture within an aqueous medium. The carbon monoxide partial pressure, the rate of consumption of carbon monoxide, the rate at which the carbon monoxide is dissolved in the reaction mixture, reaction temperature and the viscosity of the reaction mixture are selected and controlled in an interrelated way to give a high yield of 4-hydroxybutyraldehyde and reduced catalyst consumption.

Abstract: A recycle solvent for use in a metal catalysed process for the production of ethanol and/or acetaldehyde by the liquid phase reaction of methanol, carbon monoxide and hydrogen is provided. The solvent should (1) form a single phase with methanol and the liquid products of the process throughout the process; (2) be one in which the catalyst and any associated promoters are soluble; (3) have a boiling point at atmospheric pressure in excess of 120.degree. C. and (4) should be chemically stable under the reaction conditions and not interact in a deliterious manner with either the catalyst or the other components of the reaction. A preferred class of recycle solvent is sulpholane and its substituted derivatives.

Abstract: Ethanol is prepared with high selectivity from methanol, carbon monoxide and hydrogen by using cobalt phosphate as main catalyst in combination with a platinum group element as co-catalyst or without using such co-catalyst, and further with or without a phosphorus compound. Recovery of the catalyst can be carried out easily.

Abstract: This invention provides a process for converting alkanols into higher alkanols, e.g. methanol into ethanol, by contacting a basic solution comprising said alkanol in the absence of added hydrogen, with a catalyst comprising a lanthanum moiety. Preferably said catalyst further comprises a rhodium or a ruthenium moiety in combination with said lanthanum moiety. This invention further provides a novel heterogeneous catalyst system adapted for alkanol homologation, which comprises lanthanum hydroxide and a rhodium or ruthenium moiety, e.g. RhCl.sub.3 or RuCl.sub.3.

Abstract: There are disclosed compounds of formula ##STR1## having a single or a double bond in the position indicated by the dotted line and wherein:Z represents an ethylene, ethenyl or an ethynyl divalent radical;X represents a hydrogen atom or an acyl radical, derived from a linear or branched lower hydrocarbon of formula R--CO, wherein R designates a hydrogen atom or a lower alkyl group, andR.sup.1 and R.sup.2, identical or different, represent each a hydrogen atom or a linear or branched alkyl radical.Compounds (I) possess useful perfuming properties.

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: Ethanol is selectively produced from the reaction of methanol with carbon monoxide and hydrogen in the presence of a transition metal carbonyl catalyst. Methanol serves as a solvent and may be accompanied by a less volatile co-solvent. The solution includes the transition metal carbonyl catalysts and a basic metal salt such as an alkali metal or alkaline earth metal formate, carbonate or bicarbonate. A gas containing a high carbon monoxide to hydrogen ratio, as is present in a typical gasifer product, is contacted with the solution for the preferential production of ethanol with minimal water as a byproduct. Fractionation of the reaction solution provides substantially pure ethanol product and allows return of the catalysts for reuse.

Abstract: The present invention relates to a process for producing ethanol and n-propanol by reacting methanol with carbon monoxide and hydrogen at elevated pressure and temperature. A system consisting of a cobalt compound, a ruthenium compound, an iodide, and an organic phosphine serves as the catalyst. The organic phosphine contains a group having a --SO.sub.3 M, --COOM or --OSO.sub.3 M radical.

Abstract: Methods and compositions are provided for asymmetrically donating an oxygen atom to a pair of electrons to produce an asymmetric product. Specifically, a metal alkoxide is used as a catalyst, where the metal has a coordination number of at least four, and at least one, usually two, of the alkoxide groups bonded to the metal are bonded to asymmetric carbon atoms. The metal catalyst is employed in conjunction with a hydroperoxide and an alkanol having a functionality with a pair of electrons capable of accepting an oxygen atom. The resulting product is enriched in one enantiomer due to the enantioselective introduction of an asymmetric center or an enhanced rate of reaction of one of the enantiomers of a chiral alkanol.

Abstract: Ethanol is produced continuously via the carbonylation of methanol, by(a) carbonylating methanol, in a reactor R, in the presence of a carbonyl complex of a metal of group VIII of the periodic table and of a halogen compound,(b) separating, in a distillation column D1, the reactor discharge, into a top fraction comprising methyl acetate, methanol, dimethyl ether and an organohalogen compound, and into a bottom fraction comprising water, small quantities of acetic acid and the catalyst, if the latter is not in a fixed bed, the residence time being so adjusted that the greater part of the acetic acid reacts with the methanol present to give methyl acetate,(c) separating the top fraction from D1, in a distillation column D2, into a top fraction comprising small quantities of methyl acetate, methanol, dimethyl ether and the organo-halogen compound, and a bottom fraction comprising methyl acetate and methanol, and recycling the top fraction to reactor R,(d) distilling off, via the top of distillation column D3, th

Abstract: A process for producing ethanol which comprises reacting methanol, carbon monoxide and hydrogen in the presence of (a) a catalyst comprising cobalt or a cobalt compound and an alkyl phosphine as an effective component and (b) a co-catalyst comprising hydrochloric acid and in the absence of an iodide is disclosed. According to the present invention, formation of by-products becomes less and selectivity to realizable ethanol becomes higher.

Abstract: A catalyst particularly suitable for selectively producing aldehydes, particularly acetaldehyde, which comprises (1) cobalt, (2) iodine and (3) a ligand containing atoms from Group VB of the Periodic Table separated by a sterically constrained carbon-carbon bonding.

Abstract: Acetaldehyde is prepared from methanol and synthesis gas with good selectivity and yield by contacting a mixture of methanol, carbon monoxide and hydrogen with an iodide or iodine free catalyst composition comprising (1) ruthenium powder, (2) a cobalt-containing compound, (3) an amine, and (4) an onium salt or base, and heating the resulting mixture to an elevated temperature and pressure for sufficient time to produce the desired acetaldehyde, and recovering the same from the reaction mixture.

Abstract: Acetaldehyde is prepared in good yield from methanol and synthesis gas by contacting the mixture of methanol, carbon monoxide and hydrogen with an iodide or iodine-free catalyst composition comprising ruthenium powder, a cobalt-containing compound and an onium salt or base, and heating the resulting mixture to an elevated temperature and pressure for sufficient time to produce the acetaldehyde, and then recovering the same from the reaction mixture.

Abstract: Acetaldehyde is prepared in good yield from methanol and synthesis gas under mild reaction conditions by contacting a mixture of methanol, carbon monoxide and hydrogen with an iodide or iodine free catalyst composition comprising (1) ruthenium powder, (2) a cobalt-containing compound (3) a rhodium-containing compound, and (4) an onium salt or base, and heating the resulting mixture under mild temperature and pressure for sufficient time to produce the desired acetaldehyde, and then recovering the same from the reaction mixture.

Abstract: A homogeneous catalytic process wherein a gaseous or vaporized reactant stream is continuously introduced into a liquid phase mixture containing (a) a volatile precious metal catalyst, and (b) methanol and/or ethanol as reactant or reaction product, at least a portion of the volatile precious metal being continuously removed from the liquid phase mixture by the effluent gas and/or vapor stream, and such effluent stream is an integral component of a cyclic process stream and/or a vent stream discharged from the process.

Abstract: Ethanol is prepared by contacting methanol, hydrogen and carbon monoxide with a catalyst system comprising an iodide-free ruthenium-containing compound, an iodide-free quaternary phosphonium or ammonium base or salt and a halide-free cobalt-containing compound, such as cobalt(III) acetylacetone or dicobalt octacarbonyl, in the presence of a substantially inert solvent.

Abstract: A method for the production of ethanol or propanol comprising the reaction of methanol with carbon monoxide and hydrogen in the presence of a catalyst. The catalyst contains a cobalt compound, a ruthenium compound, iodine or an iodide, and a bi-dentate organic phosphine or phosphite. The reaction is carried out at 150.degree. to 250.degree. C., 200 to 600 bars, and in the presence of 5 to 25% by weight of water, based on the methanol.

Abstract: A process for producing ethanol which comprises reacting methanol, carbon monoxide and hydrogen, characterized in that the reaction is carried out in the presence of (a) a solvent selected from the group consisting of hydrocarbons, and ethers and (b) a catalyst comprising a cobalt compound, a ruthenium compound and a tertiary phosphine in the absence of iodine, bromine, an iodine compound or a bromine compound is disclosed. According to this invention, ethanol can be produced from methanol, carbon monoxide and hydrogen in a high selectivity to neat ethanol.

Abstract: A process for the production of oxygen-containing organic products from the reaction of oxides of carbon and hydrogen in the presence of a cobalt-containing compound of the formula Co.sub.3 (CO).sub.9 C--Y.

Abstract: A process for producing ethanol which comprises reacting methanol, carbon monoxide and hydrogen, characterized in that the reaction is carried out in the presence of (a) an inert solvent and (b) a catalyst containing cobalt compound, a manganese compound and a tertiary phosphine. According to the present invention, amount of by-products formed is small.

Abstract: A method of obtaining deuterated compounds from compounds having an abstractable proton comprises contacting the proton-containing compound with a porous ion exchange resin which contains at least some deuterons. The reverse process of substituting protons for deuterons in deuterated compounds is also described. Highly pure products can be obtained.

Abstract: A process for the selective formation of ethanol and methyl acetate by contacting methanol, hydrogen and carbon monoxide with a catalyst comprising rhodium and iron in the reduced state deposited on a support of alumina containing a minor amount of an alkaline metal at reaction conditions correlated so as to favor the formation of a substantial proportion of ethanol and methyl acetate.

Abstract: Ethanol is formed by contacting a mixture of carbon monoxide, hydrogen and methanol with a catalyst comprising a cobalt-containing compound and a germanium-containing compound, such as dicobalt octacarbonyl and triphenylgermanium hydride in the presence of an inert, oxygenated hydrocarbon solvent at a temperature of about 50.degree. to about 350.degree. C. and at a pressure of about 500 psig or greater.

Abstract: A novel process for selectively producing ethanol which comprises introducing into a reaction zone (1) methanol, (2) hydrogen, (3) carbon monoxide, (4) a cobalt carbonyl, a hydrido cobalt carbonyl or a cobalt-containing material convertible to a cobalt carbonyl or a hydrido cobalt carbonyl, (5) a tertiary organo Group VA compound of the Periodic Table, (6) an iodine compound and (7) a ruthenium compound; and then subjecting the contents of said reaction zone to an elevated temperature and an elevated pressure for a time sufficient to convert methanol to ethanol.

Abstract: A homogeneous catalytic process for the conversion of methanol to methyl acetate. The process comprises contacting CO with methanol in the presence of a catalytically effective amount of an iron-cobalt carbonyl complex of the formula M[FeCo.sub.3 (CO).sub.12 ] or M[CoFe.sub.3 (CO).sub.13 ] where M is hydrogen or a cation and an iodide promoter, heating the resultant mixture at temperatures of from 100.degree. to 250.degree. C. at pressures of from 5 to 100 MPa.

Abstract: Improved process for the production of acetaldehyde and ethanol by reacting methanol with carbon monoxide and hydrogen in the presence of a catalyst system containing cobalt, elemental iodine or bromine as promotor and a polydentate phosphorus, arsenic, antimony or bismuth compound using one or more metals from the group comprising chromium, molybdenum, tungsten, uranium, titanium, vanadium, iron and nickel as co-catalyst.

Abstract: Conversion of carbon monoxide, hydrogen, alcohol and olefin containing mixtures in the presence of a new class of heterogeneous catalyst is provided. Said new class of heterogeneous catalyst comprises a substrate having a minimum surface area of about 10 m.sup.2 /g and having pores with a minimum pore diameter of about 5 Angstrom Units, said substrate being modified by at least one amine functional member coordinated to a metal function, said amine functional member acting as a bridging member between said substrate and said metal function.

Abstract: Conversion of carbon monoxide, hydrogen, and alcohol containing mixtures in the presence of a new class of heterogeneous catalyst is provided. Said new class of heterogeneous catalyst comprises a substrate having a minimum surface area of about 10 m.sup.2 /g and having pores with a minimum pore diameter of about 5 Angstrom Units, said substrate being modified by at least one amine functional member coordinated to a metal function, said amine functional member acting as a bridging member between said substrate and said metal function.

Abstract: The present invention provides a process for the preparation of acetaldehyde from hydrogen, carbon monoxide, and methanol. The process comprises conducting the reaction in the presence of a catalyst system comprising cobalt, platinum, and iodide. The cobalt catalyst component is present in a concentration of about 0.01 to 1 weight percent, the platinum catalyst component is present in a concentration of about 0.03 to 3 weight percent, and the iodide catalyst component is present in a concentration of about 0.1 to 40 weight percent, as defined herein. The weight ratio of cobalt to platinum is about 1:0.3 to 1:35. The process is preferably conducted at a temperature of 160.degree.-230.degree. C. and a pressure of 10,000-70,000 kPa.

Abstract: A transition metal carbonyl and a tertiary amine are employed as a homogeneous catalytic system in methanol or a less volatile solvent to react methanol with carbon monoxide and hydrogen gas producing ethanol and carbon dioxide. The gas contains a high carbon monoxide to hydrogen ratio as is present in a typical gasifier product. The reaction has potential for anhydrous ethanol production as carbon dioxide rather than water is produced. Selected transition metal carbonyls include those of iron, rhodium ruthenium, manganese in combination with iron and possibly osmium. Selected amines include trimethylamine, N-Methylpyrrolidine, 2,4-diazabicyclooctane, dimethylneopentylamine, N-methylpiperidine and derivatives of N-methylpiperidine.