Abstract: A continuous process for efficiently co-producing secondary alcohols of long-chain olefins and lower carboxylic acid esters, comprising (I) performing an acid/olefin reaction in the presence of a heterogeneous catalyst such as Amberlyst 15, and (II) performing an ester-exchange reaction in the presence of, e.g., titanium alcoholate. A desirable feature of the process is the ability to produce co-products of choice.
Type:
Grant
Filed:
April 19, 1989
Date of Patent:
May 22, 1990
Assignee:
Union Carbide Chemicals and Plastics Company, Inc.
Inventors:
Robert J. Knopf, Louis F. Theiling Jr., Leroy P. Berti
Abstract: An efficient method is proposed for the synthesis of an unsaturated alcohol of the general formula R--CH.dbd.CH(CH.sub.2).sub.n+1 OH, in which R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms and the subscript n is an integer in the range from 3 to 10, in which an acetate of the formula R--CH.dbd.CHCH.sub.2 OCOCH.sub.3 is subjected to a coupling reaction with a Grignard reagent of the formula X.sup.1 Mg(CH.sub.2).sub.n OMgX.sup.2, in which X.sup.1 and X.sup.2 are each a halogen atom, and then the reaction product is hydrolyzed. When the reaction product of the coupling reaction is reacted with acetic anhydride instead of hydrolysis, the corresponding acetate can readily be obtained. These unsaturated alcohols and acetates form a class of important biologically active compounds or intermediates thereof including sex pheromone compounds of insects.
Abstract: A process for the preparation of ethyltrifluoroacetoacetate is provided. In this first step, ethyltrifluoroacetate is condensed with ethyl acetate in the presence of sodium ethoxide in cyclohexane. In a second step, the condensation product is neutralized with a protonic acid, such as formic acid, to release an enol. In the third step, the ethyltrifluoroacetoacetate obtained is separated by distillation. The ethyltrifluoroacetoacetate is used as an intermediate in syntheses in the pharmaceutical or plant protection industry.
Abstract: A process for the production of a dialkyl carbonate, e.g. dimethyl carbonate, or a dialkyl oxalate, e.g. dimethyl oxalate, from butane, oxygen carbon monoxide and an alcohol is provided in a series of integrated process steps. In the case of a dialkyl oxalate, the product can be hydrogenated further to produce an ether of ethylene glycol.
Abstract: A process for the production of a dialkyl carbonate, e.g. dimethyl carbonate, or a dialkyl oxalate, e.g. dimethyl oxalate, from butane, oxygen, carbon monoxide and an alcohol is provided in a series of integrated process steps. In the case of a dialkyl oxalate, the product can be hydrogenated further to produce an ether of ethylene glycol.
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: A catalyst suitable for use in reactions catalyzed by strong base is provided. The catalyst comprises an organic compound containing a Group VA element for example an amine or phosphine supported on a solid which is insoluble in the reaction mixture. The catalyst may be activated by treatment with an epoxide. Catalysts in which the amine is an amidine or a guanidine are particularly effective.
Abstract: Disclosed is a process for preparing metal cyanates by reacting an alkyl carbamate having the formula ##STR1## wherein R is a lower alkyl group having 1 to 4 carbon atoms with an alkali metal hydride or an alkaline earth metal hydride.
Abstract: In a process for preparing a nitroalcohol by reacting a nitroparaffin and an aldehyde in a solvent, the improvement comprising the use of 0.5 to 5 mole percent of a trialkyl phosphine, based on the nitroparaffin, which greatly reduces reaction time to 0.1 to 5 hours.
Abstract: An alcohol and carbon monoxide are produced by the decarbonylation of an alkyl formate in the presence of, as catalyst, (i) a Lewis base and epoxide or (2) an amidine or a guanidine. When the Lewis base used is a trivalent phosphorus compound, for example a phosphine, it is preferable to have alcohol present at the start of the reaction.
Abstract: Process for the preparation of terminally unsaturated alcohols by the thermal decomposition of a polycarbonate in the presence of titanium containing catalyst.
Type:
Grant
Filed:
September 27, 1982
Date of Patent:
May 8, 1984
Assignee:
National Distillers and Chemical Corporation
Abstract: Disclosed is a process for converting a carbohydrate or lactic acid feedstock into an ethanol product in the presence of a metal salt at a reaction temperature ranging from about 250.degree. to about 400.degree. C. The improvement comprises establishing a reaction mixture of said feedstock, said metal salt, water, and an organic solvent. The organic solvent has a boiling point above about 150.degree. C., is stable at the reaction temperature, and solvates said feedstock. The solvent is selected from the group consisting of an alcohol, an ether, a tertiary amine, an amine oxide, a quaternary ammonium hydroxide, and a sulfoxide.
Abstract: The invention is a process for the preparation of a 2-phenylethyl alcohol which comprises contacting an aromatic aldehyde with carbon monoxide and hydrogen in a solvent comprising an oxygenated polar hydrocarbon and water, in the presence of a catalytic amount of a catalyst comprising a cobalt compound, a ruthenium salt and an iodine salt, at elevated temperatures and a pressure of between 600 and 45,000 psi.
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: A preparation of a plasticizer alcohol, consisting of predominantly 2-propylheptanol, from linear butenes is described in which oxo product of the butenes is aldoled to condense n-pentaldehyde therein with very little cross-aldolization followed by hydrogenation to obtain the 2-propylheptanol with very small 2-propyl-4-methyl hexanol content. The alcohol product as phthalate ester has excellent plasticizer properties. Also processes are described for converting other olefins to alcohols by oxo, aldol and hydrogenation reactions, with particular attention to converting hexenes obtained by propylene dimerization to C.sub.14 alcohols suitable for preparation of detergents.
Abstract: Polyhydroxylated compounds such as glucose, sucrose, sorbitol, etc. are subjected to a hydrogenolysis reaction at hydrogenolysis conditions which include a temperature in the range of from about 175.degree. to about 250.degree. C. and a pressure in the range of from about 10 to about 2000 pounds per square inch in the presence of a catalytic composition of matter. The catalyst comprises a carbonaceous pyropolymer possessing recurring units containing at least carbon and hydrogen atoms which is impregnated with a transition metal. The products which are obtained will include alcohols, acids, ketones, ethers, and hydrocarbons.
Abstract: .beta., .gamma.-Dihydropolyprenyl alcohols of the general formula: ##STR1## wherein n represents an integer of 8 to 10, exhibit hypotensive activity and anti-hepatic disease-activity.
Abstract: A homogeneous catalytic process for the decarbonylating of formate esters to alcohols and carbon monoxide. The process comprises contacting formate esters of the formula HCOOR where R is C.sub.1 -C.sub.10 aliphatic, C.sub.7 -C.sub.14 araliphatic or C.sub.6 -C.sub.10 aryl with a copper complex of the formula Cu(L)X where L is CO, phosphine or phosphite and X is the anion of an acid in an inert atmosphere at temperatures of from about 100.degree. to 300.degree. C.
Abstract: Carbon monoxide of high purity and methanol can be obtained from a mixture of methyl formate and methanol without eliminating methanol or isolating methyl formate from the mixture by selectively pyrolyzing methyl formate alone in the presence of an alkali metal compound other than alkali metal alcoholates.
Abstract: In a process for the preparation of a carboxylic acid ester of .beta.-formyl-crotyl alcohol by rearrangement of the corresponding carboxylic acid ester of 2-formyl-2-hydroxy-but-3-ene or of an acetal or acylate thereof in the presence of copper or a copper compound, followed, where relevant, by hydrolytic cleavage of the acetal or acylate, more especially in the preparation of 4,4-dimethoxy-3-methyl-crotyl acetate, the yield is improved by carrying out the rearrangement in the presence of copper (I) chloride as the catalyst and ensuring that low-boiling by-products formed during the rearrangement are removed.The products are of great importance as starting materials for an industrial synthesis of vitamin A and its derivatives.
Type:
Grant
Filed:
August 31, 1979
Date of Patent:
November 17, 1981
Assignee:
BASF Aktiengesellschaft
Inventors:
Harald Laas, Axel Nissen, Bernd Meissner
Abstract: A process for producing .omega.-alkene-1-ols which comprises reacting an .alpha.,.omega.-alkanediol having 4 to 14 carbon atoms with a fatty acid selected from the group consisting of stearic acid, palmitic acid and a mixture of stearic acid and palmitic acid.
Abstract: Anthranilic acid has been anchored to polystyrene, and rhodium, palladium, platinum and ruthenium complexes of this modified polystyrene have been prepared. These catalysts will reduce a variety of olefinic and aromatic hydrocarbons, and also nitrile, nitro and carbonyl functional groups, said carbonyl groups being present in either ketones or aldehydes.
Type:
Grant
Filed:
March 29, 1979
Date of Patent:
December 9, 1980
Assignee:
Western Kentucky University
Inventors:
Norman L. Holy, William A. Logan, Karl D. Stein