Abstract: Ethanol is produced by reacting methanol with carbon dioxide and hydrogen at a temperature in the range 150.degree. to 250.degree. C., a pressure in the range 100 to 300 bars and a residence time in the range 10 minutes to 8 hours in the presence of:(i) a cobalt-containing catalyst optionally promoted with iodine, bromine or an organo-phosphorus compound and optionally in the presence of a stabilizer and,(ii) an additive which may be a monocarboxylic acid and/or a derivative thereof and, optionally, a non-polar solvent such as an alkane, benzene or an alkyl-substituted benzene.The preferred additives are acetic acid and methyl acetate. The presence of the additive increases the total realizable yield and selectivity to ethanol.

Abstract: Ethanol is prepared by contacting methanol, hydrogen and carbon monoxide with a catalyst system comprising a ruthenium compound, a quaternary phosphonium or ammonium base or salt and a cobalt compound such as cobalt iodide.

Abstract: Ethanol is prepared by contacting methanol, hydrogen and carbon monoxide with a catalyst system comprising a ruthenium compound, a quaternary phosphonium or ammonium base or salt and a cobalt compound such as cobalt iodide in the presence of a non-polar, substantially inert, oxygenated hydrocarbon solvent.

Abstract: A process for selectively preparing ethanol by contacting methanol, hydrogen and carbon monoxide with a solid catalyst comprising rhodium and iron in the reduced state deposited on a support of alumina impregnated with a promoter amount of a heterocyclic amine at reaction conditions correlated so as to favor the formation of a substantial proportion of ethanol.

Abstract: A process for selectively preparing ethanol by contacting methanol, hydrogen and carbon monoxide with a solid catalyst comprising rhodium and iron in the reduced state deposited on a support of alumina impregnated with a promoter amount of a heterocyclic amine at reaction conditions correlated so as to favor the formation of a substantial proportion of ethanol.

Abstract: A process for the production of a product comprising ethanol which process comprises reacting at elevated temperature and pressure and in the liquid phase methanol with hydrogen and carbon monoxide in the presence of an inert, particulate solid comprising a high surface area form of silica, alumina, silica/alumina or carbon, a methanol soluble catalyst comprising either:(i) cobalt as the sole catalytic metal entity added either: as cobalt carbonyl or bis (triphenylphosphine) iminium tetracarbonylcobaltate or in a form capable of forming a carbonyl and/or carbonyl hydride complex under the prevailing reaction conditions, or(ii) a metal of Group VIII of the Periodic Table excluding iron, palladium and platinum as the sole catalytic metal entity added either as a metal complex in which the ligand is derived from cyclopentadiene or a substituted cyclopentadiene of formula: ##STR1## in which R is independently hydrogen, methyl or ethyl, or in a form capable of forming the complex under the prevailing reaction cond

Abstract: In a process for the production of ethanol and n-propanol by conversion of methanol with carbon monoxide and hydrogen in the presence of a catalyst containing cobalt, platinum, at least one halogen or halide, and an organic phosphine or phosphite, the improvement comprising the halogen or halide being chlorine or a chloride, and the phosphine or phosphite being bidentate. In addition, the conversion is carried out at pressures of 200 to 800 bars in the presence of 5 to 25% by weight of water, based on the methanol.

Abstract: A process for selectively producing alcohols, particularly ethanol, which comprises introducing into a reaction zone (1) methanol, (2) carbon monoxide, (3) hydrogen, (4) cobalt, (5) iodine, (6) ruthenium and (7) a ligand containing atoms from Group VA of the Periodic Table separated by a sterically constrained carbon-carbon bond, 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 said ethanol.

Abstract: A process for selectively producing ethanol which comprises introducing into a reaction zone methanol, hydrogen, carbon monoxide, a cobalt tricarbonyl complex and an iodine promoter and then subjecting the contents of said reaction zone to an elevated temperature and an elevated pressure for a time period sufficient to convert methanol to ethanol.

Abstract: Methanol can be selectively converted to acetaldehyde, ethanol or mixtures thereof, using a homogeneous process. The process comprises contacting methanol with carbon monoxide and hydrogen in the presence of a catalytic system containing cobalt-ruthenium complexes or a soluble ruthenium compound plus Co.sub.2 (CO).sub.8-n where n is from 0 to 4.

Abstract: Process for manufacturing a constituent for motor car gasoline from a synthesis gas containing essentially carbon dioxide, carbon monoxide and hydrogen, comprising producing methanol and its higher homologs by treatment of said synthesis gas in a first catalytic reaction zone at 230.degree.-350.degree. C., cooling and condensing the effluent therefrom, separating from the liquid condensate a gas fraction, treating the latter at 240.degree.-300.degree. C. in a second catalytic reaction zone to produce a liquid methanol fraction and admixing said methanol fraction with said liquid condensate to form said gasoline constituent.

Abstract: A novel catalyst system comprising (1) a cobalt carbonyl, a hydrido cobalt carbonyl or a cobalt-containing material convertible to a cobalt carbonyl or a hydrido cobalt carbonyl, (2) a tertiary organo Group VA compound of the Periodic Table, (3) an iodine compound and (4) a ruthenium compound and to a 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: Rose oxide, which is an important olfactive compound valuable in the art of perfumery, is advantageously produced from citronellol through a novel synthetic route comprising(1) anodic alkoxylation of citronellol using as a supporting electrolyte an alkali metal aromatic sulfonate,(2) dealkoxylation of the resulting 2,6-dimethyl-3-alkoxyoct-1-en-8-ol in the presence of a palladium or nickel complex, and then(3) cyclization of the resulting dehydrocitronellol in the presence of an acid.

Abstract: C.sub.4 compounds including n-butanol and n-butanal are produced by reacting methanol, hydrogen, and carbon monoxide, in the presence of a cobalt catalyst selected from the group consisting of (a) a cobalt carbonyl, (b) a hydrido cobalt carbonyl and (c) a cobalt-containing material convertible to a cobalt carbonyl or a hydrido cobalt carbonyl, an iodine promotor and a biphosphine disulfide having the formula: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4, the same or different, are selected from the group consisting of saturated or unsaturated, staight or branched chain alkyl radicals having from one to 24 carbon atoms, cycloalkyl radicals having from three to 40 carbon atoms, aryl radicals having from six to 20 carbon atoms, aralkyl and alkaryl radicals having from six to 40 carbon atoms and halogen substituted derivatives thereof.

Abstract: A process and catalyst system for selectively producing n-butanol and n-butanal which process comprises introducing into a reaction zone methanol, hydrogen, carbon monoxide and a catalyst system consisting essentially of (a) a cobalt carbonyl, a hydrido cobalt carbonyl or a cobalt-containing material convertible to a cobalt carbonyl or a hydrido cobalt carbonyl, (b) an iodine compound and (c) a tertiary organo Group VA 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 n-butanol and n-butanal.

Abstract: C.sub.4 compounds including n-butanol and n-butanal are produced by reacting methanol, hydrogen, and carbon monoxide, in the presence of a cobalt catalyst selected from the group consisting of (a) a cobalt carbonyl, (b) a hydrido cobalt carbonyl and (c) a cobalt-containing material convertible to a cobalt carbonyl or a hydrido cobalt carbonyl, an iodine promotor and a thiol defined by the formula:RSHwherein R is selected from the group consisting of saturated or unsaturated, straight or branched chain alkyl radicals having from one to 24 carbon atoms, cycloalkyl radicals having from three to 40 carbon atoms, aryl radicals having from six to 20 carbon atoms, aralkyl and alkaryl radicals having from six to 40 carbon atoms and halogen substituted derivatives thereof. A high degree of selectivity towards the formation of butanol and butanal is provided by using the cobalt entity and the thiol in a molar ratio in the range of about 2:1 to about 10:1, based on elemental cobalt and sulfur.

Abstract: C.sub.4 compounds including n-butanol and n-butanal are produced by reacting methanol, hydrogen, and carbon monoxide, in the presence of a cobalt catalyst selected from the group consisting of (a) a cobalt carbonyl, (b) a hydrido cobalt carbonyl and (c) a cobalt-containing material convertible to a cobalt carbonyl or a hydrido cobalt carbonyl, an iodine promotor and an organic sulfide having the formula:R.sub.1 --S--R.sub.2wherein R.sub.1 and R.sub.2 can be the same or different members selected from the group consisting of saturated or unsaturated, straight or branched chain alkyl radicals having from one to 24 carbon atoms, cycloalkyl radicals having from three to 40 carbon atoms, aryl radicals having from six to 20 carbon atoms, aralkyl and alkaryl radicals having from six to 40 carbon atoms and halogen substituted derivatives thereof.

Abstract: Ethanol and/or acetaldehyde are produced by reacting at elevated temperature and pressure methanol with synthesis gas in the presence of a catalyst comprising a metal complex in which the metal is a metal of Group VIII of the Periodic Table other than iron, palladium and platinum and the ligand is derived from cyclopentadiene or a substituted cyclopentadiene and a promoter which is an iodide or a bromide. Optionally there is also added as a co-promoter a compound of formula X(A) (B) (C) wherein X is nitrogen, phosphorus, arsenic, antimony or bismuth and A, B and C are individually C.sub.1 to C.sub.20 monovalent hydrocarbyl groups which are free from aliphatic carbon-carbon unsaturation and are bound to the X atom by a carbon/X bond, or X is phosphorus, arsenic, antimony or bismuth and any two of A, B and C together form an organic divalent cyclic ring system bonded to the X atom, or X is nitrogen and all of A, B and C together form an organic trivalent cyclic ring system bonded to the X atom, e.g.

Abstract: Disclosed is an improved process for the homologation of alkanols to obtain the next higher alkanol homolog by the cobalt-catalyzed reaction of an alkanol reactant with carbon monoxide and hydrogen under homologation conditions. The improvement comprises carrying out the homologation process in the presence of a perfluorocarboxylate anion.

Abstract: A process for the homologization of methanol to produce ethanol, comprising carbonylating methanol in the simultaneous presence of hydrogen, cobalt, ruthenium, at least one ionic halide, and at least one alkyl halide, the molar ratio Ru/Co being at least about 2.

Abstract: A homogeneous catalytic process for the selective conversion of methanol to ethanol or acetaldehyde. The process comprises contacting CO and H.sub.2 with a catalytically effective amount of an iron-cobalt carbonyl complex of the formula M[FeCo.sub.3 (CO).sub.12 ] where M is hydrogen or a cation and an iodide promoter; heating the resulting mixture at temperatures of from 100.degree. to 250.degree. C. at pressures of from 5 to 100 MPa. By controlling the reaction parameters of H.sub.2 :CO ratio, temperature and reaction time, acetaldehyde or ethanol can be selectively produced.

Abstract: Ethanol is produced by reacting methanol with hydrogen and carbon monoxide at elevated temperature and pressure in the presence of a catalyst comprising cobalt, and iodide or a bromide and a compound having X(A)(B)(C) in which formula X is a nitrogen or phosphorus and A, B and C are individually monovalent organic radicals, or X is phosphorus and any two of A,B and C together form an organic divalent cyclic ring system bonded to the X atom, or X is nitrogen and all of A,B and C form an organic trivalent cyclic ring system bonded to the X atom, and in the additional presence of an added inert liquid which is characterized as a compound capable of forming, under normal conditions of temperature and pressure, a separate phase in the presence of methanol containing up to 20% w/w water, which compound contains in its structure bonds other than carbon/carbon and carbon/hydrogen.

Abstract: The invention relates to the production of oxygenated organic compounds comprising alcohols, aldehydes, ethers and salts of carboxylic acids. Prior art processes for the production of ethanol in particular involve the use of elevated temperatures and pressures. Milder conditions can be used in the process of the invention in which either a mercury compound of formula (R.sup.1 OCHR.sup.2 CHR.sup.3 Hg).sub.n X (I), wherein X is an organic or inorganic anion, n is an integer equal to the valency of the anion, R.sup.2 and R.sup.3 are independently a hydrogen atom or an alkyl group and R.sup.1 is a hydrogen atom, an alkyl group or the group --(--CHR.sup.2 CHR.sup.3 Hg).sub.n X, or the precursors of the compound (I), with a catalyst comprising a complex containing a metal of Group VIII, particularly rhodium, in the presence of a liquid reagent containing an active acidic hydrogen atom. A particularly suitable rhodium complex is one having the formula:[Rh(C.sub.5 Me.sub.5).sub.2 (OH).sub.3 ]Cl.xH.sub.

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 produced with a good selectivity and good conversion from methanol, carbon monoxide and hydrogen by conducting reaction in the presence of a cobalt sulfide or a mixture of a cobalt sulfide and at least one of a nitrogen-containing compound and a phosphorus compound.

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. The only other significant by product is methane. Selected transition metal carbonyls include those of iron, ruthenium and possibly manganese and osmium. Selected amines include trimethylamine, N-Methylpyrrolidine, 24-diazabicyclooctane, dimethyneopentylamine and 2-pryidinol.

Abstract: An improved process is described for synthetically converting methanol to ethanol in which a mixture of methanol and cobalt catalyst is pre-pressurized with an atmosphere of carbon monoxide at room temperature and at a pressure of about 10 to 1000 psi gauge, in a suitable pressure vessel. A gaseous mixture of carbon monoxide/hydrogen, in the stoichiometric 1:2 molar ratio, is then introduced to react with the methanol/cobalt catalyst mixture and the temperature is raised to about 175.degree. to 240.degree. C. at a pressure of about 3000-6000 psig. The improved process leads to higher selectivities of ethanol formation with lowered amounts of by-products.

Abstract: A process for the production of ethanol from the cobalt-catalyzed, iodide-promoted reaction of methanol, hydrogen and carbon monoxide, attaining selectivity to ethanol heretofore unachievable at high methanol conversion, wherein the reaction is carried out in an inert solvent, at a temperature of from greater than 180.degree. C. to 220.degree. C. with an iodide to cobalt mole ratio of from 0.1:1 to 4:1.

Abstract: Ethanol and/or acetaldehyde is (are) produced by reacting methanol and synthesis gas at elevated temperature and pressure in the presence of a catalyst consisting of (a) cobalt, (b) an iodide or a bromide and (c) a polydentate ligand wherein the donor atoms are selected from nitrogen, phosphorus, arsenic, antimony and bismuth, ethanol being the predominant product when the donor atoms are exclusively nitrogen or phosphorus, particularly phosphorus, and acetaldehyde being the major product when the donor atoms are exclusively arsenic, antimony or bismuth. A particularly effective polydentate ligand is one having the formula:(R.sup.1)(R.sup.2)X--[C(R.sup.5)(R.sup.6)].sub.n --Y(R.sup.3)(R.sup.4) (II)in which X and Y are independently nitrogen, phosphorus, arsenic, antimony or bismuth; n is an integer; (R.sup.1), (R.sup.2), (R.sup.3) and (R.sup.4) are independently saturated monovalent organic radicals containing from 1 to 20 carbon atoms.

Abstract: A process for allylic rearrangement, particularly terpenoid allylic rearrangement, utilizing certain acid forming metals to form an ester or alcoholate (alcohologen) of the allylic alcohol to be rearranged, isomerizing and cleaving the alcohologen in the presence of a transition metal compound catalyst and recovering the rearranged alcohol.

Abstract: A process for selectively producing ethanol which comprises introducing into a reaction zone (1) methanol, (2) hydrogen, (3) carbon monoxide, (4) a cobalt tricarbonyl complex, (5) an iodine compound and (6) 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 process for selectively producing ethanol which comprises introducing into a reaction zone methanol, hydrogen, carbon monoxide, a cobalt tricarbonyl complex and an iodine promoter and then subjecting the contents of said reaction zone to an elevated temperature and an elevated pressure for a time period sufficient to convert methanol to ethanol.

Abstract: A process for producing ethanol from the reaction of methanol, hydrogen and carbon monoxide catalyzed by a phosphine-iodine promoted cobalt-ruthenium catalyst, the improvement of maintaining the phosphine to halide ratio and concentration within a critical range, and whereby the concentration of phosphine compound in the reaction mixture is increased without causing an undesirable decrease in the activity of the catalyst; thereby obtaining a highly stable and active catalyst providing an increased selectivity to ethanol formation. This is accomplished under such conditions that the catalyst stability is maintained and the ratio of phosphine to halide is kept at a relatively constant value during the reaction.

Abstract: Synthesis of an attractant (11Z,13Z)-11,13-hexadecadienal for the navel orangeworm Amyelois transitella, and intermediates therefor.

Abstract: Ethanol is produced by reacting methanol with carbon monoxide and hydrogen at temperatures in the range 150.degree. to 250.degree. C. and pressures greater than 100 bar in the presence of a cobalt catalyst and an additive which is miscible with methanol containing up to 20% w/w water, which additive is an alcohol, an aldehyde, a ketone or an ether. Particular additives are n-propanol, n-butanol, acetone, acetaldehyde, 1,4-dioxane, tetrahydrofuran, di-n-propylether and diphenyl ether. Optionally the catalyst is promoted with iodine or bromine or preferably both iodine or bromine and an organo-phosphorous compound. Other additives such as non-polar solvents, acids and derivatives thereof and inert liquids can be incorporated in the reaction mixture.

Abstract: A process for the reacting of methanol with carbon monoxide and hydrogen to produce increased amounts of methyl acetate, acetaldehyde and dimethyl acetal utilizing a catalyst comprising a cobalt carbonyl in complex with an organic nitrogen ligand.

Abstract: In the cobalt carbonyl-catalyzed carbonylation of methanol to ethanol, acetaldehyde and methyl acetate, a tertiary phosphine oxide is utilized as a stabilizer. Product is distilled from the reaction mixture and the cobalt-containing residue solution is recycled.

Abstract: A novel process is described for the preparation of novel organic solutions of organooxy magnesium compounds of low viscosity, which solutions are formed in the presence of at least 5 mol % based on the magnesium compound of an organooxy compound of a transition metal of Groups IV through VI of the Periodic Table.

Abstract: This invention relates to an improvement in a process for producing ethanol by methanol homologation. The homologation is carried out by reacting methanol with hydrogen and carbon monoxide in a 1-2:1 mole ratio and a temperature of from about 175-230.degree. C. and a pressure of 2,000-10,000 psig in the presence of a cobalt catalyst represented by formulas I and II.

Abstract: An improvement in the process wherein carbon monoxide and hydrogen are reacted in the liquid phase in the presence of a cobalt carbonyl catalyst whereby increased amounts of ethanol may be produced, which improvement comprises conducting the reaction in the presence of a non-polar, substantially inert, oxygenated hydrocarbon solvent.

Abstract: This invention provides an improved process for converting methanol into ethanol and ethanol precursors with higher efficiency than prior art methods. This invention further provides a novel heterogeneous co-catalyst system adapted for alkanol homologation which consists essentially of cobalt carbonyl and rhenium metal.

Abstract: A process for the selective formation of ethanol which comprises contacting methanol, hydrogen and carbon monoxide with a catalyst system comprising cobalt acetylacetonate, a tertiary organo Group V A compound of the periodic Table, a first promoter comprising an iodine compound and a second promoter comprising a ruthenium compound.

Abstract: An improved process is described for converting methanol to ethanol in which a mixture of methanol, liquid water and a Group VIII metal catalyst and a basic inorganic compound is contacted with an atmosphere of carbon monoxide at a temperature of about 240.degree. to 280.degree. C and a pressure of about 3,000-5,000 psi gauge. Good yields and selectivities of ethanol are obtained eliminating the necessity of using gaseous hydrogen or steam as starting materials, as required in prior art processes.

Abstract: A process for the synthesis of perfume products, Vitamin E and intermediates described herein involving a coupling reaction. For instance, a process for the synthesis of dehydrophytol and Vitamin E comprising forming a C.sub.15 acetylene from hexahydropseudoionone and then coupling said acetylene with 1-acetoxy-4-chloro-3-methylbut-2-ene to form a C.sub.20 acetoxy-enyne. The latter is readily subjected to partial hydrogenation and saponification in that order to form a dehydrophytol, a useful intermediate for the synthesis of Vitamin E and other products.

Abstract: Structural modification of olefinically unsaturated alcohols is achieved by contacting the unsaturated alcohol under reaction conditions with a catalytic amount of a catalyst composition comprising a ruthenium hydride complex of tertiary phosphine ligands.

Abstract: This invention provides an improved process for converting methanol into ethanol and ethanol precursors with higher efficiency than prior art methods. This invention further provides a novel heterogeneous co-catalyst system adapted for alkanol homologation which consists essentially of cobalt carbonyl and rhenium metal.

Abstract: Process for production of ethylenic compounds by hydrogenating the corresponding alkynol with isopropyl alcohol in the presence of a metal complex such as IrH.sub.3 CO(P.phi..sub.3).sub.2 and IrH.sub.3 (P.phi..sub.3).sub.2.