Method for selective hydrogenation of unsaturated aldehydes

FIELD: chemistry.

SUBSTANCE: invention relates to a method for producing saturated aldehydes by contacting a liquid organic feed containing unsaturated aldehydes with hydrogen or hydrogen-containing gas in presence of crustal catalyst comprising palladium particles of not more than 6 nm in size, applied in form of a layer not thicker than 150 microns on exterior surface of porous alumina carrier granules. Herewith the carrier has not less than 60% of pores with a diameter of 5 to 50 nm, and the hydrogenation is carried out at a liquid feed rate of 1-4 h-1.

EFFECT: producing target products with high selectivity at high process efficiency and feedstock conversion.

25 cl, 8 dwg, 6 tbl, 6 ex

 



 

Same patents:

FIELD: chemistry.

SUBSTANCE: installation comprises: sources of synthesis-gas and olefins, connected to reactor via purification devices, successively connected by means of pipelines with reactor input gas-liquid separator and evaporator, collector of bottom residue of which is connected with reverse pipeline of liquid recycle, with output of aldehydes from evaporator being collected with rectification column via collector-separator, as well as unit for discharge of waste catalyst and heavy reaction products. Installation is provided with sensor of liquid level, installed in collector of bottom residue; device for preparation of fresh catalyst solution, connected with reverse pipeline of liquid recycle and made in form of mixer with dosing device of catalyst components, with unit for discharge of waste catalyst and heavy reaction products being made in from of successively connected pump with device of its switching on and off, meter of liquid flow, device for distilling aldehydes from waste catalyst solution and connected with meter of liquid flow and dosing device of catalyst components of actuator, with output for aldehydes from device for their distillation from waste catalyst solution being connected with mixer of device for preparation of fresh catalyst solution, and sensor of liquid level is located with device of pump switching on and off.

EFFECT: realisation of hydroformylation on claimed installation makes it possible to provide constant optimal quantity of heavy reaction products, optimal composition and quantity of catalyst solution.

1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of regulating hydroformylation process for obtaining aldehydes of normal structure (N) and iso-structure (I) with ratio N:I. Claimed method includes contact of unsaturated olefin compound with synthesis-gas and catalyst, which contains transition metal and organopolyphosphite and organomonophosphite ligand, with contact being carried out in conditions of hydroformylation, including partial pressure of synthesis-gas, where method includes increase of partial pressure of synthesis-gas to reduce ratio N:I or reduction of partial pressure of synthesis-gas to increase ratio N:I.

EFFECT: obtaining aldehydes of normal structure (N) and iso-structure (I) with ratio N to I.

10 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of hydroformylation and can be used in chemical industry. Claimed is method of hydroformylation for obtaining aldehyde product, including interaction in mode of continuous reaction in liquid phase for hydroformylation of unsaturated olefin compounds, carbon monoxide and hydrogen in presence of mixture of triphenylphosphine and organo-bisphosphite ligand of formula , where R1 and R2 represent monovalent aryl radical, containing from 6 to 40 carbon atoms, R28 represents C1-20-alkyl or cycloalkyl radical or alkoxyradical; and R29 can represent hydrogen atom, C1-20-alkyl or cycloalkyl radical or alkoxyradical. One of said ligands binds with rhodium with formation of hydroformylation catalyst, with molar ratio of triphenyl to metal and organo-bisphosphite ligand to metal constituting at least 4.

EFFECT: presence of organomonophosphite in said system of catalysts based on Rh/organopolyphosphite complex results in catalysts stabilisation without loss of reaction rate.

10 cl, 5 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to regioselective obtaining of n-pentanal, which is used for obtaining plasticisers, additives to motor oils, synthetic lubricating materials. The method is realised in a medium of an aldehyde-containing solvent by the interaction of synthesis-gas with an industrial butane-butene fraction in the presence of a catalytic system, containing rhodium and a diphosphite ligand, with the reaction being carried out with the content of the aldehyde in the solvent not less than 10 wt %, at temperatures 80-110°C, total pressure 0.7-3 MPa, synthesis-gas pressure 0.5-2.5 MPa, with a molar ratio of hydrogen to carbon oxide being in the range 5.0-0.5, molar ratio diphosphite/Rh being in the range 3-15, and rhodium concentration constituting 30-300 ppm, and the addition into a reaction mixture of antioxidants, selected from bisphenols of general formulas: the content of which constitutes 10-40 mol per 1 g-at. rhodium, where R stands for hydrocarbon univalent radicals or hydrogen.

EFFECT: elaboration of a method of regioselective obtaining of n-pentanal.

1 tbl, 26 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a novel acyclic aldehyde having 16 carbon atoms, containing at least three branches and selected from a group consisting of: 3-ethyl-7,11-dimethyldodecanal, 2,3,7,11-tetramethyl-dodecanal, 7,11,-dimethyl-3-vinyldodeca-6,10-dienal and 4,8,12-dimethyltrideca-4,7,11-trienal, to a composition of substances suitable for use as starting material for producing surfactants and containing at least one of the disclosed acyclic aldehydes, to a composition of detergent alcohols, suitable for producing a composition of surfactants and containing at least one acyclic alcohol converted from the disclosed acyclic aldehyde, and to a surfactant composition suitable for use in a detergent or cleaning composition and containing one or more surfactant derivatives of isomers of the acyclic detergent alcohol converted from the disclosed acyclic aldehyde. The invention also relates to versions of a cleaning composition and to versions of a method of producing an alcohol mixture for a composition of detergent alcohols.

EFFECT: improved properties of compounds.

19 cl, 10 tbl, 24 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing aldehydes via hydroformylation of terminal or internal olefins in the presence of a catalyst system containing rhodium and a mono- or polyphosphite ligand. An antioxidant is added to the reaction mixture, the antioxidant being phenols or thioureas of general formulae: where R denotes identical or different aliphatic or aromatic univalent radicals or hydrogen, and hydroformylation is carried out in liquid phase in a solvent medium in form of aldehyde, with rhodium concentration of 0.1-2 mmol/l, at temperature of 20-150°C and pressure of 0.2-5 MPa, wherein the amount of the antioxidant is 1-30 mol/mol phosphite ligand.

EFFECT: invention enables to obtain end products using an efficient method at low raw material costs.

2 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of processing a hydroformylation reaction liquid product which contains an aldehyde, high-boiling hydroformylation reaction by-products, a homogeneously dissolved rhodium complex catalyst, an unreacted olefinically unsaturated compound, synthesis gas and volatile by-products, in which a) the liquid stream after hydroformylation is throttled in an expansion tank, wherein there is separation into a liquid phase and a gas phase, b) the liquid phase obtained in the expansion tank is fed into a separation device in which there is separation into a liquid phase, which mainly contains high-boiling hydroformylation reaction by-products, a homogeneously dissolved rhodium complex catalyst and a small amount of aldehyde, and a gas phase which contains the bulk of the aldehyde, and c) a liquid rhodium-containing stream is collected from the separation device. A portion of the liquid rhodium-containing output stream collected from the separation device is removed from the process and the other portion is passed through a filter, and the separated solid substances are removed from the process while the obtained filtrate is returned to the hydroformylation reaction.

EFFECT: method enables to prevent breakdown and/or deactivation of the hydroformylation catalyst.

13 cl, 1 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method for direct conversion of lower C1-C4 paraffins to oxygenates such as alcohols and aldehydes, which are valuable intermediate products of organic synthesis and can be used as components of engine fuel and/or starting material for producing synthetic gasoline and other engine fuels. The method involves passing a mixture consisting of a lower paraffin or oxygen, diluted with an inert gas or air or pure oxygen, through a catalyst bed at temperature not higher than 350°C. The catalyst used is a catalyst system for heterogeneous reactions, which contains microfibre of a high-silica support and at least one active element, the active element being in form of either a MeOxHalv composite or a EwMezOxHaly composite, wherein the element Me in both composites is selected from a group which includes transition metals of groups 5-12 and periods 4 and 5, or elements of lanthanum or lanthanide groups or, preferably, ruthenium; element Hal is one of the halogens: fluorine, chlorine, bromine, iodine, but preferably chlorine; element E in the EwMezOxHaly composite is selected from a group which includes alkali, alkali-earth elements, or hydrogen, and indices w, z, x and y are weight fractions of elements in given composites and can vary in the following ranges: z - from 0.12 to 0.80, x - from 0.013 to 0.34, y - from 0.14 to 0.74, w - from 0 to 0.50.

EFFECT: method enables to achieve high degree of conversion of starting reactants and high selectivity of formation of alcohols.

4 cl, 15 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a continuous hydroformylation process for producing a mixture of aldehydes with improved control over normal/branched (N/I) isomer ratio of the product aldehydes. The method involves contacting under continuous reaction conditions in a hydroformylation reaction fluid, one or more olefin compounds, carbon monoxide and hydrogen in the presence of a mixture of an organopolyphosphite ligand and an organomonophosphite ligand, at least one of said ligands being bonded to a transition metal to form a hydroformylation catalyst containing a transition metal-ligand complex; the organopolyphosphite ligand comprising a plurality of phosphorus (III) atoms each bonded to three hydrocarbyloxy radicals, any non-bridging species of which consists essentially of an aryloxy radical (substituted or unsubstituted); the contacting is further conducted: (a) at a sub-stoichiometric molar ratio of organopolyphosphite ligand to transition metal such that said molar ratio is greater than 0 but less than 1.0/1; (b) at a super-stoichiometric molar ratio of organomonophosphite ligand to transition metal such that said molar ratio is greater than 2/1; (c) at a carbon monoxide partial pressure in a negative order region of a hydroformylation rate curve wherein rate of reaction decreases as carbon monoxide partial pressure increases, and wherein rate of reaction increases as carbon monoxide partial pressure decreases, the rate curve being measured on an identical hydroformylation process in the presence of the organopolyphosphite ligand but not the organomonophosphite ligand; and (d) with varying the molar ratio of organopolyphosphite ligand to transition metal within the aforementioned sub-stoichiometric range while maintaining the molar ratio of organomonophosphite ligand to transition metal in the aforementioned super-stoichiometric range, so as to control continuously the normal/branched isomer ratio of the aldehyde products.

EFFECT: providing a continuous production of a mixture of aldehydes with improved control over normal/branched (N/I) isomer ratio of the aldehyde products.

21 cl, 3 ex, 4 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a carbonylation method in which at least one compound olefinically unsaturated compound reacts with carbon monoxide in the presence of a complex catalyst of a metal of subgroup VIII of the periodic table of elements, containing an organophosphorus compound as a ligand, where the additional reagent used is at least hydrogen and hydroformylation is carried out. Carbonylation is carried out in the presence of at least one sterically hindered secondary amine with 2,2,6,6-tetramethylpiperidine , units. The invention also relates to a mixture for use in the disclosed carbonylation method.

EFFECT: invention enables to obtain desired products with high selectivity using a stable catalyst system.

18 cl, 4 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of hydrogenating α,β-unsaturated ketones of general formula , where R1, R2=H or R1-R2=-(CH2)3-, which includes hydrogenating benzal alkanone with hydrogen gas in a solvent medium in the presence of a catalyst. The benzal alkanone used is benzalacetone or benzalcyclohexanone, and the catalyst used is colloidal nickel particles obtained by reducing nickel (II) chloride with lithium aluminium hydride, and the process is carried out at atmospheric pressure of hydrogen in a tetrahydrofuran medium at 55-60°C.

EFFECT: invention enables to obtain saturated ketones with high output using a simple method.

2 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to a method of obtaining saturated aliphatic ketone, represented by the general formula (2), (where n stands for an integer number from 1 to 3; R represents a hydroxyl group, a cyclohexyl group, an alkyl group, which has from 1 to 4 carbon atoms, or an acyl group, which has from 1 to 4 carbon atoms), applied as an initial material for the production of medications, agrochemical preparations, optic functional materials and functional materials for electronics. The method consists in hydrogenation of a nucleus of an aromatic ketone, represented by the general formula (1), (where n stands for an integer number from 1 to 3; R represents a hydroxyl group, a phenyl group, an alkyl group, which has from 1 to 4 carbon atoms, or an acyl group, which has from 1 to 4 carbon atoms), with hydrogen under pressure in the presence of a solvent at a temperature from 20 to 120°C and in the presence of a catalyst, which carries from 0.1 to 20 wt % of the ruthenium atom on a carrier.

EFFECT: method makes it possible to obtain the target product with high selectivity.

6 cl, 24 ex

FIELD: chemistry.

SUBSTANCE: method involves Wittig olefination of the 6E-isomer of 2E-2,6-dimethyl-8-triphenylsilyloxyocta-2,6-dien-4-yn-1-al (synthon C10)ylid, generated in situ from β-cyclogeranyltriphenyl phosphonium halide, removal of triphenylsilyl protection in the obtained silylated 13E-isomer of 11,12-didehydroretinol. After removal triphenylsilyl protection, the obtained 13E-isomer of 11,12-didehydroretinol is oxidised to 11,12-didehydroaldehyde using MnO2 without extracting the semi-product separately and further purification procedures, and stereo-specific reduction of the triple bond in 11,12-didehydroaldehyde is then carried out in via hydrogenation on a Lindlar catalyst to obtain the desired 11-cis-retinal isomer, where generation of ylide from β-cyclogeranyltriphenyl phosphonium halide is carried out under the following conditions: a) NaH in tetrahydrofuran at 0-5°C, b) anhydrous K2CO3 in dichloromethane, in the presence of interphase transfer catalysts - quaternary ammonium salts at 20-25°C, or c) 1,2-epoxybutane in dichloromethane at 50-60°C.

EFFECT: obtaining medicinal agents for preventing or therapy of severe pathologies of the human optical system.

2 cl, 1 dwg, 1 tbl, 5 ex

FIELD: organic chemistry, chemical chemistry.

SUBSTANCE: invention relates to a method for synthesis of compound of the formula (I): . Method involves interaction of compound of the formula (II)

with compound of the formula (III) in the presence of a catalyst chosen from cationic complexes of bivalent ruthenium and polar organic solvent. Also, invention relates to a novel compound of the formula (I) that is used in synthesis of phyton and vitamin E, and to a method for synthesis of phyton also.

EFFECT: improved method of synthesis.

20 cl, 3 ex

The invention relates to a method for producing 4,4-dimethyl-1-(p-chlorophenyl)pentane-3-one, which is an intermediate product to obtain pesticides and pharmaceutical products, including tebuconazole

FIELD: organic chemistry, chemical chemistry.

SUBSTANCE: invention relates to a method for synthesis of compound of the formula (I): . Method involves interaction of compound of the formula (II)

with compound of the formula (III) in the presence of a catalyst chosen from cationic complexes of bivalent ruthenium and polar organic solvent. Also, invention relates to a novel compound of the formula (I) that is used in synthesis of phyton and vitamin E, and to a method for synthesis of phyton also.

EFFECT: improved method of synthesis.

20 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: method involves Wittig olefination of the 6E-isomer of 2E-2,6-dimethyl-8-triphenylsilyloxyocta-2,6-dien-4-yn-1-al (synthon C10)ylid, generated in situ from β-cyclogeranyltriphenyl phosphonium halide, removal of triphenylsilyl protection in the obtained silylated 13E-isomer of 11,12-didehydroretinol. After removal triphenylsilyl protection, the obtained 13E-isomer of 11,12-didehydroretinol is oxidised to 11,12-didehydroaldehyde using MnO2 without extracting the semi-product separately and further purification procedures, and stereo-specific reduction of the triple bond in 11,12-didehydroaldehyde is then carried out in via hydrogenation on a Lindlar catalyst to obtain the desired 11-cis-retinal isomer, where generation of ylide from β-cyclogeranyltriphenyl phosphonium halide is carried out under the following conditions: a) NaH in tetrahydrofuran at 0-5°C, b) anhydrous K2CO3 in dichloromethane, in the presence of interphase transfer catalysts - quaternary ammonium salts at 20-25°C, or c) 1,2-epoxybutane in dichloromethane at 50-60°C.

EFFECT: obtaining medicinal agents for preventing or therapy of severe pathologies of the human optical system.

2 cl, 1 dwg, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to a method of obtaining saturated aliphatic ketone, represented by the general formula (2), (where n stands for an integer number from 1 to 3; R represents a hydroxyl group, a cyclohexyl group, an alkyl group, which has from 1 to 4 carbon atoms, or an acyl group, which has from 1 to 4 carbon atoms), applied as an initial material for the production of medications, agrochemical preparations, optic functional materials and functional materials for electronics. The method consists in hydrogenation of a nucleus of an aromatic ketone, represented by the general formula (1), (where n stands for an integer number from 1 to 3; R represents a hydroxyl group, a phenyl group, an alkyl group, which has from 1 to 4 carbon atoms, or an acyl group, which has from 1 to 4 carbon atoms), with hydrogen under pressure in the presence of a solvent at a temperature from 20 to 120°C and in the presence of a catalyst, which carries from 0.1 to 20 wt % of the ruthenium atom on a carrier.

EFFECT: method makes it possible to obtain the target product with high selectivity.

6 cl, 24 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of hydrogenating α,β-unsaturated ketones of general formula , where R1, R2=H or R1-R2=-(CH2)3-, which includes hydrogenating benzal alkanone with hydrogen gas in a solvent medium in the presence of a catalyst. The benzal alkanone used is benzalacetone or benzalcyclohexanone, and the catalyst used is colloidal nickel particles obtained by reducing nickel (II) chloride with lithium aluminium hydride, and the process is carried out at atmospheric pressure of hydrogen in a tetrahydrofuran medium at 55-60°C.

EFFECT: invention enables to obtain saturated ketones with high output using a simple method.

2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing hexahydro-iso-alpha-acids from iso-alpha-acids (or tetrahydro-iso-alpha-acids), which includes mixing iso-alpha-acids (or tetrahydro-iso-alpha-acids) with a heterogeneous ruthenium-containing catalyst, which catalyses hydrogenation of iso-alpha-acids or tetrahydro-iso-alpha-acids to obtain hexahydro-iso-alpha-acids, in the absence of a solvent or in the presence of a solvent phase (e.g., carbon dioxide, water, ethanol or other organic solvent or mixtures thereof) and in the absence or in the presence of other hop compounds (such as beta-acids). The obtained mixture is then exposed to a temperature at which the reaction medium, which contains an iso-alpha-acid (or tetrahydro-iso-alpha-acid), has a sufficiently low viscosity to be easily mixed with the heterogeneous ruthenium-containing catalyst, and held in an atmosphere containing hydrogen over a reaction time sufficient for efficient conversion of the reactant, which is an iso-alpha-acid (or tetrahydro-iso-alpha-acid), into a hexahydro-iso-alpha-acid.

EFFECT: methods enable to obtain end products with high selectivity and without using an extra reduction step using an inorganic reducing agent.

21 cl, 2 dwg, 10 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for producing saturated aldehydes by contacting a liquid organic feed containing unsaturated aldehydes with hydrogen or hydrogen-containing gas in presence of crustal catalyst comprising palladium particles of not more than 6 nm in size, applied in form of a layer not thicker than 150 microns on exterior surface of porous alumina carrier granules. Herewith the carrier has not less than 60% of pores with a diameter of 5 to 50 nm, and the hydrogenation is carried out at a liquid feed rate of 1-4 h-1.

EFFECT: producing target products with high selectivity at high process efficiency and feedstock conversion.

25 cl, 8 dwg, 6 tbl, 6 ex

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